CN103333484B - Hydrophobic medical thermoplastic polyurethane alloy - Google Patents
Hydrophobic medical thermoplastic polyurethane alloy Download PDFInfo
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- CN103333484B CN103333484B CN201310302169.8A CN201310302169A CN103333484B CN 103333484 B CN103333484 B CN 103333484B CN 201310302169 A CN201310302169 A CN 201310302169A CN 103333484 B CN103333484 B CN 103333484B
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- thermoplastic polyurethane
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- hydrophobic
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 41
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 38
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 38
- 229920006347 Elastollan Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005452 bending Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008520 organization Effects 0.000 abstract 1
- 230000004936 stimulating effect Effects 0.000 abstract 1
- 235000019589 hardness Nutrition 0.000 description 30
- 239000000463 material Substances 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000000638 stimulation Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- DSUFPYCILZXJFF-UHFFFAOYSA-N 4-[[4-[[4-(pentoxycarbonylamino)cyclohexyl]methyl]cyclohexyl]carbamoyloxy]butyl n-[4-[[4-(butoxycarbonylamino)cyclohexyl]methyl]cyclohexyl]carbamate Chemical compound C1CC(NC(=O)OCCCCC)CCC1CC1CCC(NC(=O)OCCCCOC(=O)NC2CCC(CC3CCC(CC3)NC(=O)OCCCC)CC2)CC1 DSUFPYCILZXJFF-UHFFFAOYSA-N 0.000 description 4
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 235000019633 pungent taste Nutrition 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002627 tracheal intubation Methods 0.000 description 1
Abstract
The invention discloses a hydrophobic medical thermoplastic polyurethane alloy which comprises acomponent A and a component B, wherein the component A is commercial medical level hydrophobic thermoplastic polyurethane with shore hardness of 65 to 78 D, which takes 55% to 90% of the alloy total weight; the component B is commercial medical level hydrophobic thermoplastic polyurethane with shore hardness of 75 to 95 D, which takes 10% to 45% of the alloy total weight. The characteristic of hardness of the component A can be maintained when the medical thermoplastic polyurethane alloy is stored in indoor temperature dry environment, after entering into the human body, the medical thermoplastic polyurethane alloy can absorb moisture which takes 1.0% to 5.0% of the medical thermoplastic polyurethane alloy weight and can be softened; compared with the storage, the modulus is declined by more than 70%. The raw material of the hydrophobic medical thermoplastic polyurethane alloy is wide, the preparation is simple, the hardness is high in indoor temperature environment, and the stimulating degree to organization can be reduced, and the hydrophobic medical thermoplastic polyurethane alloy can resist bending and is favor of involving in human body, can be softened in the human body obviously and is suitable for preparing medical interventional catheter.
Description
Technical field
The invention belongs to the technical field of modification of medical thermoplastic polyurethane, be specifically when preserving under a kind of drying at room temperature environment hardness high, enter human body after the Hydrophobic medical thermoplastic polyurethane alloy that can significantly soften.
Background technology
Medical introducing duct field has the applicating history of decades.In intervention procedure, conduit generally needs the draw point being beneficial to skin puncture by could enter smoothly in human body or blood vessel.However, still require that the material manufacturing conduit especially small size conduit has higher hardness, in order to ensure that conduit retraction does not occur and improves disposable intervention success ratio.After also requiring that conduit enters human body, there is enough flexibilities simultaneously, reduce the stimulation degree of conduit to tissue or vessel wall, reduce the occurrence probability getting involved the complication such as site inflammation, pain, thrombus and medicinal liquid osmosis.
Tetrafluoroethylene and fluorinated ethylene-propylene multipolymer are medical introducing duct materials the most common, this material hardness is higher, be beneficial to puncture, but after entering human body, hardness does not change substantially, very strong to the pungency of tissue, also there is the phenomenon of easily bending blocking liquid in this kind of material simultaneously clinically.
For fluorinated plastic Problems existing, people have disclosed multiple solution.As U.S. Patent Publication No. 4950257 discloses a kind of compound interposing catheter, the tip of this conduit adopts the blend preparation of soft nylon elastomer/nylon 11, object to be reduce conduit to the stimulation degree of tissue; Catheter main body adopts the nylon of hard, polyethylene or polypropylene material to prepare, and ensures not bounce back in intubation intervention process.But this composite conduit needs to prepare tip and main body respectively, then the two is fused into entirety, therefore in use, be difficult to thoroughly avoid disengaging that is most advanced and sophisticated and main body, add the risk of breakage of conduit.
Another kind of solution adopts polyurethane for medical introducing duct, this is because urethane has biocompatibility excellence, resistance to bending, breaking tenacity is high and form and can carry out the advantage such as regulating in a big way.Through the development of decades, existing a lot of companies supply (as companies such as Bayer, BASF and Lu Borun) interposing catheter medical grade polyurethane raw material at present.But these urethane all well can not be applied to medical introducing duct, main drawback is: higher to the stimulation destructiveness of tissue because of not softening significantly after the urethane that hardness is high enters human body; The urethane that hardness is low can not meet intervention requirement because of too soft, gets involved success ratio low.In fact, the polyurethane material being applicable to preparing interposing catheter now is all through special synthesis and obtains, as U.S. Patent Publication No. 4883699 and 5102401 etc. adopts hydrophilic polyurethane material to prepare interposing catheter, such conduit has very high hardness when preserving in dry environment, after entering human body, can occur swelling by quick adsorption water molecules, modulus obviously reduces.Because conduit diameter obviously increases after but such conduit is swelling, cause the pressure increase that tissue is subject to, limit the practical application of this kind of conduit.U.S. Patent Publication No. 5281677 discloses a kind of polyurethane blends, when conduit prepared by this blend is placed at ambient temperature, there is the hardness being beneficial to puncture, and after entering human body, hardness can decline 75-88%, and water absorption and swelling phenomenon can not occur, thus considerably reduce the stimulation degree of conduit to tissue.Regrettably two kinds of urethane raws for the preparation of this polyurethane blends all need to synthesize preparation especially, limited source.
Summary of the invention
Technical problem to be solved by this invention is the deficiency overcoming restriction medical introducing duct polyurethane material, provide a kind of raw material sources extensively, prepare simple, resistance to bending, at ambient temperature hardness high, be beneficial to and get involved human body, can obviously soften and alleviate the Hydrophobic medical thermoplastic polyurethane alloy to tissue stimulation degree in human body.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of Hydrophobic medical thermoplastic polyurethane alloy, and its composition comprises:
Component A: be the medical grade hydrophobic type thermoplastic polyurethane of shore hardness between 65-78D, account for the 55-90% of alloy gross weight;
B component: be the medical grade hydrophobic type thermoplastic polyurethane of shore hardness between 75-95A, account for the 10-45% of alloy gross weight.
Component A of the present invention is the medical grade hydrophobic type thermoplastic polyurethane of a kind of shore hardness between 65-78D or the blend of the medical grade hydrophobic type thermoplastic polyurethane of more than one shore hardnesses between 65-78D.The medical grade hydrophobic type thermoplastic polyurethane material of preferred shore hardness between 70-78D.
B component of the present invention is the medical grade hydrophobic type thermoplastic polyurethane of a kind of shore hardness between 75-95A or the blend of the medical grade hydrophobic type thermoplastic polyurethane of more than one shore hardnesses between 75-95A.The medical grade hydrophobic type thermoplastic polyurethane material of preferred shore hardness between 80-85A.
In Hydrophobic medical thermoplastic polyurethane alloy of the present invention, component A hardness is higher, and content is higher, plays the effect of dispersion medium; B component content is low to be surrounded by component A as disperse phase.Like this under drying at room temperature environment, the reactivity of the molecular chain of softer B component limit by A, make alloy retain the hardness of component A, shore hardness is between 65-78D.This Hydrophobic medical thermoplastic polyurethane alloy is in the physiological saline of 37 ° of C, and the water-intake rate in 24 hours is the 1.0-5.0% of its weight.After alloy enters human body, envrionment temperature is elevated to 37 ° of about C, urethane adsorbs a small amount of moisture (about 1-5%) gradually simultaneously, add the reactivity of the molecular chain of component A, now the reactivity of the molecular chain of B component is no longer by the restriction of component A, and strengthening the reactivity of the molecular chain of component A further, alloy is occurred obviously softening, modulus rate of descent can reach more than 70%.The present invention can be prepared by the mode melt extruding blended or solution blending, and preferred molten extrudes blending method.Time blended, the medical grade additives such as appropriate oxidation inhibitor, antiseptic-germicide and lubricant can be added.
The present invention adopts business-like medical grade hydrophobic polyurethane to be raw material, the raw materials used medical grade non-toxic product, in large supply be through certification; Alloy preparation for processing is simple.For the preparation of medical introducing duct, products obtained therefrom meets resistance to bending required by medical introducing duct, good biocompatibility and to the Property requirements such as tissue pungency is little.Against existing technologies, raw material sources of the present invention extensively, prepare simple, resistance to bending, at ambient temperature hardness high, be beneficial to and get involved human body, can obviously soften and alleviate tissue stimulation degree in human body.Be a kind of desirable Hydrophobic medical thermoplastic polyurethane alloy, be applicable to prepare medical introducing duct.
Embodiment
Below in conjunction with concrete embodiment, the present invention is further described, but scope of the present invention is not limited in these examples.
Embodiment 1: take component A medical grade hydrophobic type thermoplastic polyurethane Tecoflex EG-72D and B component medical grade hydrophobic type thermoplastic polyurethane Tecoflex EG-85A respectively by 90/10 weight ratio.Tecoflex EG-72D is that Lubrizol Corp. produces, and shore hardness is 67D.Tecoflex EG-85A is that Lubrizol Corp. produces, and shore hardness is 77A.The two is mixed 5 minutes in high-speed mixer, then transfers to 80 ° of dry 4-6 hour of C in hopper-type dehumidifying device, obtain dry pack.Dry pack is joined in twin screw extruder, carry out melting mixing, the screw diameter of forcing machine is 36mm, length-to-diameter ratio is 28/1, setting forcing machine is 140-180 ° of C from material mouth to the temperature of mouth mould, die temperature is 180 ° of C, and blend, through die extrusion, cooling, pelletizing, obtains polyurethane alloys.Test shows that this alloy modulus in flexure (GB/T9341-2000) when 23 ° of C is 670MPa, and in 37 ° of C water after 24 hours, modulus in flexure reduces to 112MPa, and water-intake rate is 2.4%.Can be used for preparing medical introducing duct.
Embodiment 2: take component A medical grade hydrophobic type thermoplastic polyurethane Elastollan 1174D and B component medical grade hydrophobic type thermoplastic polyurethane Elastollan 1185A respectively by 55/45 weight ratio.Elastollan 1174D provides for BASF AG produces, shore hardness 73D.Elastollan 1185A provides for BASF AG produces, shore hardness 85A.The two is mixed 5 minutes in high-speed mixer, then transfers to 110 ° of dry 3-5 hour of C in hopper-type dehumidifying device, obtain dry pack.Dry pack is joined in twin screw extruder, carry out melting mixing, the screw diameter of forcing machine is 36mm, length-to-diameter ratio is 28/1, setting forcing machine is 190-215 ° of C from material mouth to the temperature of mouth mould, die temperature is 215 ° of C, and blend, through die extrusion, cooling, pelletizing, obtains polyurethane alloys.Test shows that this alloy modulus in flexure (GB/T9341-2000) when 23 ° of C is 564MPa, and in 37 ° of C water after 24 hours, modulus in flexure reduces to 92MPa, and water-intake rate is 3.0%.Be applicable to prepare medical introducing duct.
Embodiment 3: take component A medical grade hydrophobic type thermoplastic polyurethane Pellethane 2363-75D and B component medical grade hydrophobic type thermoplastic polyurethane Pellethane 2363-80A respectively by 70/30 weight ratio.Pellethane 2363-75D is that Lubrizol Corp. produces, shore hardness 76D.Pellethane 2363-80A is that Lubrizol Corp. produces, shore hardness 81A.The two is mixed 5 minutes in high-speed mixer, then transfers to 110 DEG C of dry 3-5 hour in hopper-type dehumidifying device, obtain dry pack.Dry pack is joined in twin screw extruder, carry out melting mixing, the screw diameter of forcing machine is 36mm, length-to-diameter ratio is 28/1, setting forcing machine is 190-215 ° of C from material mouth to the temperature of mouth mould, die temperature is 215 ° of C, and blend, through die extrusion, cooling, pelletizing, obtains polyurethane alloys.Test shows that this alloy modulus in flexure (GB/T9341-2000) when 23 ° of C is 726MPa, and in 37 ° of C water after 24 hours, modulus in flexure reduces to 150MPa, and water-intake rate is 2.5%.Can be used for preparing medical introducing duct.
Embodiment 4: take medical grade hydrophobic type thermoplastic polyurethane Elastollan 1174D and Elastollan 1164D respectively by 80/20 weight ratio.Elastollan 1174D and Elastollan 1164D is that BASF AG produces, shore hardness 64D.The two is mixed 5 minutes in high-speed mixer, transfer to 110 ° of dry 3-5 hour of C in hopper-type dehumidifying device again, join in twin screw extruder, carry out melting mixing, setting forcing machine is 190-215 ° of C from material mouth to the temperature of mouth mould, prepares medical grade hydrophobic type thermoplastic polyurethane alloy component A.
Medical grade hydrophobic type thermoplastic polyurethane Elastollan 1180A and Elastollan 1185A is taken respectively by 50/50 weight ratio.Elastollan 1180A and Elastollan 1185A is that BASF AG produces, shore hardness 80A, the two is mixed 5 minutes in high-speed mixer, transfer to 90 ° of dry 3-5 hour of C in hopper-type dehumidifying device again, join in twin screw extruder, carry out melting mixing, setting forcing machine is 165-190 ° of C from material mouth to the temperature of mouth mould, prepares medical grade hydrophobic type thermoplastic polyurethane alloy B component.
Above-mentioned component A and B component is taken respectively by 85/15 weight ratio, the two is mixed 5 minutes in high-speed mixer, transfer to 110 ° of dry 3-5 hour of C in hopper-type dehumidifying device again, join in twin screw extruder, carry out melting mixing, the screw diameter of forcing machine is 36mm, length-to-diameter ratio is 28/1, and setting forcing machine is 190-215 ° of C from material mouth to the temperature of mouth mould, and die temperature is 215 ° of C, blend, through die extrusion, cooling, pelletizing, obtains polyurethane alloys.Test shows that this alloy modulus in flexure (GB/T9341-2000) when 23 ° of C is 535MPa, and in 37 ° of C water after 24 hours, modulus in flexure reduces to 85MPa, and water-intake rate is 3.1%.Be applicable to prepare medical introducing duct etc.
Claims (2)
1. a Hydrophobic medical thermoplastic polyurethane alloy, is characterized in that composition comprises:
Component A: be the medical grade hydrophobic type thermoplastic polyurethane of shore hardness between 72-78D, account for the 55-80% of alloy gross weight;
B component: be the medical grade hydrophobic type thermoplastic polyurethane of shore hardness between 85-95A, account for the 20-45% of alloy gross weight.
2. Hydrophobic medical thermoplastic polyurethane alloy according to claim 1, is characterized in that described component A to be shore hardness is the medical grade hydrophobic type thermoplastic polyurethane Elastollan 1174D of 74D, account for 55% of alloy total amount; B component is the medical grade hydrophobic type thermoplastic polyurethane Elastollan 1185A of 85A, accounts for 45% of alloy gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310302169.8A CN103333484B (en) | 2013-07-18 | 2013-07-18 | Hydrophobic medical thermoplastic polyurethane alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310302169.8A CN103333484B (en) | 2013-07-18 | 2013-07-18 | Hydrophobic medical thermoplastic polyurethane alloy |
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| CN103333484A CN103333484A (en) | 2013-10-02 |
| CN103333484B true CN103333484B (en) | 2015-06-24 |
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| CN201310302169.8A Active CN103333484B (en) | 2013-07-18 | 2013-07-18 | Hydrophobic medical thermoplastic polyurethane alloy |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110802825B (en) * | 2019-11-12 | 2020-09-15 | 北京化工大学 | Preparation method of medical catheter with ultrasonic capability and product thereof |
| CN115337472B (en) * | 2022-08-30 | 2023-08-29 | 中国科学院长春应用化学研究所 | Coating composition, coating, preparation method of coating and medical device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387199A (en) * | 1992-02-24 | 1995-02-07 | Baxter International Inc. | Polymer blends for torque transmitting catheters |
| EP0962227A1 (en) * | 1998-06-02 | 1999-12-08 | Terumo Kabushiki Kaisha | Indwelling catheter |
| CN103127557A (en) * | 2013-02-22 | 2013-06-05 | 广州健恩医疗设备有限公司 | Medical polyurethane catheter |
-
2013
- 2013-07-18 CN CN201310302169.8A patent/CN103333484B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387199A (en) * | 1992-02-24 | 1995-02-07 | Baxter International Inc. | Polymer blends for torque transmitting catheters |
| EP0962227A1 (en) * | 1998-06-02 | 1999-12-08 | Terumo Kabushiki Kaisha | Indwelling catheter |
| CN103127557A (en) * | 2013-02-22 | 2013-06-05 | 广州健恩医疗设备有限公司 | Medical polyurethane catheter |
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| CN103333484A (en) | 2013-10-02 |
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