CN103483610B - Preparation method for medical polymer material with blood compatibility - Google Patents
Preparation method for medical polymer material with blood compatibility Download PDFInfo
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- CN103483610B CN103483610B CN201210194481.5A CN201210194481A CN103483610B CN 103483610 B CN103483610 B CN 103483610B CN 201210194481 A CN201210194481 A CN 201210194481A CN 103483610 B CN103483610 B CN 103483610B
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Abstract
The present invention discloses a preparation method for a medical polymer material with blood compatibility, wherein under a vacuum condition, inert gas ions are injected into the surface of a polymer material to form a carbon chain structure having C=C bond and C[triple-bond]C bond so as to finally obtain the medical polymer material with blood compatibility. According to the present invention, operations of the method are simple, physical and chemical structures of the material are not affected, and the medical film obtained after the treatment has characteristics of stable surface structure and excellent blood compatibility.
Description
Technical field
The present invention relates to a kind of preparation method of medical polymer material with blood compatibility, belong to Surface Modification of Medical Polymer Materials field.
Background technology
Current, medical macromolecular materials are widely used in the material with contacting blood.Wherein, et al. Ke macromolecular material has artificial blood vessel, vascular suture line, artificial heart valve, benefit hernia sheet, artificial bone's equivalent material etc.; Extracorporeal blood contact macromolecular material has blood bag, hemostix, blood transfusion tube, extracorporeal circulation of blood etc.With contacting blood process, in order to avoid there is material thrombus, blood coagulation phenomenon, requiring that material has excellent blood compatibility, comprising and have less adhesive capacity to blood platelet, do not activate thrombin, even do not destroy blood rbc, thus be conducive to blood circulation or storage.Under so strict requirement, can choice for use can the medical macromolecular materials of contacting blood relatively less.The macromolecular material that the blood compatibility used at present is good has silicon rubber, tetrafluoroethylene, polyvinylidene difluoride (PVDF) etc.But, even if these materials have blood compatibility relatively preferably, in use also need to add the anticoagulation medicines such as a certain amount of heparin and carry out Anti-coagulation blood effect.Meanwhile, limited material category limits the range of choice of biomechanical property.Therefore, in the urgent need to inventing a kind of new technology, existing medical macromolecular materials being modified, improving the material surface characteristic with contacting blood, improving its blood compatibility, thus widen kind and the use range of blood compatibility material.
Current, in the grafting of a large amount of employing material surface, the anticoagulin such as heparin, albumin gives its surperficial blood compatibility.As, king enters (number of patent application: 200910216683.3,201110195704.5) adopt pulsed plasma polymerization at intravascular stent deposited on silicon plasma polymerization allylamine function film, to be soaked in heparin sodium mixed solution heparin in grafting subsequently, to obtain a kind of preparation method of anticoagulant intravascular stent.For another example, cold auspicious (number of patent application: 200810045103.4) utilize plasma immersion and ion implantation device radio frequency discharge process inorganic material surface forever, be immersed in after process in the albumin or heparin solution that concentration is 10 ~ 100MG/ML, reach the anticoagulant effect of material surface.But these methods are all based on metallic substance or ceramic, by physico-chemical process at its surface deposition one deck function film, often low, the complex process of efficiency, easily introduce hazardous property small-molecule substance.
Plasma surface modifying method adopts physical means modified macromolecule material Surface Physical Chemistry structure, as the people such as Huang Nan (application number: 00817704.X, 200510062706.1) utilize plasm immersion ion implantation to form diamond thin or TiO2-x film to improve its blood compatibility at material surface.But although this method is simply effective to metal or ceramic, but there is layer and easily come off in the macromolecular material softer to matrix, there is the risk introducing hazardous property small-molecule substance.The people such as Liu Xianghuai (application number: 01139159.6) adopt N
+ion implantation RESEARCH OF PYROCARBON, improves its surperficial blood compatibility.Although this invention adopts inject N
+ion improves its blood compatibility, but it only processes the good RESEARCH OF PYROCARBON of blood compatibility own, is not suitable for the finishing of other baroque macromolecular materials.
Therefore, need to provide a kind of method that can provide the macromolecular material with blood compatibility, it is by modifying polymer surface chemical structure, thus improves the surperficial blood compatibility of macromolecular material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of medical polymer material with blood compatibility; By under vacuum, inert gas ion is injected into polymer surface, forms the carbon-chain structure of C=C and C ≡ C key, finally obtain medical polymer material with blood compatibility; The method is simple to operate, does not affect the physicalchemical structure of material body, and the medical macromolecular materials surface tissue obtained after process is stablized, and has excellent blood compatibility.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of medical polymer material with blood compatibility, it comprises the following steps:
(1) medical macromolecular materials are put into ion implantation device, be evacuated to pressure not higher than 5.0 × 10
-2pa;
(2) pass into rare gas element, pressure is not higher than 1.0 × 10
-2pa, inert gas plasma is injected into medical macromolecular materials surface, implantation dosage is no less than 1.0 × 10
15ions/cm
2, injecting the degree of depth is 0.0001 ~ 1 μm; Wherein, described rare gas element is argon gas and/or helium.
Described inert gas plasma is the charged ion that argon gas and/or helium generate.
Further, described medical macromolecular materials comprise polyethylene, polypropylene, polystyrene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly(lactic acid), polycaprolactone, polyhydroxyalkanoate, nylon, urethane, polyether-ether-ketone, gather dioxy ring ethyl ketone, silicon rubber etc.
Further, the preparation method of described medical polymer material with blood compatibility also comprises: (3), after inert gas plasma injection terminates, pressure is not higher than 1.0 × 10
-2pa, inject nitrogen plasma, implantation dosage is 0.0001 ~ 1.0 × 10
18ions/cm
2, injecting the degree of depth is 0.0001 ~ 1 μm.
Further, described nitrogen plasma is N
2, NH
3, N
2and H
2, NH
3and H
2, or N
2and NH
3the charged ion generated.Wherein, N
2and H
2, NH
3and H
2, or N
2and NH
3can mix with arbitrary proportion.
After nitrogen plasma is injected medical macromolecular materials, the molecular structure generation chemical reaction of nitrogen and medical macromolecular materials, produces a large amount of nitrogenous chemical group.
Further, the preparation method of described medical polymer material with blood compatibility also comprises: (3), after inert gas plasma injection terminates, pressure is not higher than 1.0 × 10
-2pa, Implanted Titanium plasma body, implantation dosage is 1.0 × 10
14~ 9.0 × 10
18ions/cm
2, injecting the degree of depth is 0.0001 ~ 0.5 μm.
Described titanium plasma body refers to the electrically charged titanium ion that titanium metal generates.
Further, the preparation method of described medical polymer material with blood compatibility also comprises: (4), after the injection of titanium plasma body terminates, pressure is not higher than 1.0 × 10
-2pa, continue to inject oxygen plasma, implantation dosage is 1.0 × 10
14~ 2.0 × 10
19ions/cm
2, injecting the degree of depth is 0.0001 ~ 0.5 μm.
Described oxygen plasma refers to the electrically charged oxonium ion that oxygen generates.
After titanium plasma body and/or oxygen plasma inject medical macromolecular materials, they interact with the carbon-chain structure of macromolecular material, generation (TiOx) C film.
Herein, when blood compatibility refers to blood and medical macromolecular materials, haemolysis does not occur, thrombin activates phenomenon, and thrombocyte is less or do not assemble at surface aggregation.
The present invention has following beneficial effect:
1, the present invention utilizes medical macromolecular materials itself to be the feature of carbon-chain structure, inert gas ion is injected its surface, the atom such as existing hydrogen, oxygen in sputtering or bombardment carbochain, a large amount of C=C, C ≡ C key carbochains is generated at macromolecule surface, form the physicalchemical structure of similar RESEARCH OF PYROCARBON, overcome the dependence to the chemical structure of medical macromolecular materials own, in use, only need select suitable inert gas ion injection technology, just can obtain the physicalchemical structure of similar RESEARCH OF PYROCARBON.
2, the macromolecular material of process of the present invention is that subsequent selective modification of surfaces physicalchemical structure provides consistent Physical chemistry of polymer surfac structure, the modification of sequent surface physicalchemical structure is the coating generated based on the carbochain of macromolecular chain own instead of foreign aid's carbon, this is conducive to stability and the persistence of modified layer, also overcomes employing vapour deposition and prepares the shortcoming that carbon-coating easily generates small molecules objectionable impurities (as containing C-N group small molecules).
3, the medical macromolecular materials upper layer obtained after process of the present invention and macromolecule matrix do not have obvious layering, Stability Analysis of Structures, difficult drop-off, give the blood compatibility of medical macromolecular materials excellence.
4, the present invention is by by N~+ implantation medical macromolecular materials surface, injects the carbochain generated and reacts to each other, form nitrogenous functional group at polymer surface, improve blood compatibility and the biocompatibility of macromolecular material with inert gas ion.
5, the present invention is by titanium and O +ion implanted medical macromolecular materials surface, injects the carbochain generated and reacts to each other, form TiOx film, improve the blood compatibility of macromolecular material at polymer surface with inert gas ion.
6, the present invention is simple to operate, does not affect the physicalchemical structure of material body.
Accompanying drawing explanation
Fig. 1 is the blood compatibility polythene material that embodiment 1 obtains.
Fig. 2 is the Raman spectrogram of the blood compatibility polyethylene nonwoven that embodiment 1 obtains.
Fig. 3 is the blood compatibility polyethylene nonwoven surface platelet adhesion reaction situation map that embodiment 1 obtains.
Fig. 4 is the blood compatibility polypropylene surface platelet adhesion reaction situation map that embodiment 2 obtains.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further described.
Embodiment 1
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 1.0mm by thickness, size is that the medical polyethylene non-woven fabrics of 10.0cm × 10.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 2.5 × 10
-3pa, passes into argon gas, and pressure maintains 1.0 × 10
-2pa, opens gas source power supply, acceleration voltage 2.5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by Ar+ion implantation to material surface, injection length is 5min, and implantation dosage is 2 × 10
15ions/cm
2, inject after terminating, turn off all power supplys of gas source, and take out material after keeping 10min under an argon atmosphere, obtain blood compatibility polyethylene nonwoven.
Fig. 1 is the pictorial diagram of blood compatibility polyethylene nonwoven after process.
Fig. 2 is the Raman spectrogram on the blood compatibility polyethylene nonwoven surface that embodiment 1 obtains, at 1550cm in the Raman spectrogram of the rear sample of process
-1and 2110cm
-1there is stronger peak in place, belongs to the peak of C=C and C ≡ C key respectively, proves the generation of material surface a large amount of C=C and C ≡ C key after processing.
Fig. 3 is the blood compatibility polyethylene nonwoven surface platelet adhesion reaction situation that embodiment 1 obtains, and obviously can find out that the polyethylene nonwoven after process does not almost have platelet adhesion reaction from figure; Hemolytic experiment test is carried out to it, finds that the hemolysis rate of the rear polyethylene nonwoven of process is all lower than 0.01%.
Embodiment 2
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.2mm by thickness, size is that the polypropylene for medical article sheet material of 5.0cm × 10.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 1 × 10
-3pa, passes into argon gas, and pressure maintains 1.0 × 10
-3pa, opens gas source power supply, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 500v condition under by Ar+ion implantation to material surface, injection length is 10min, and implantation dosage is 4 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and turn off argon gas after keeping 10min under an argon atmosphere; Pass into nitrogen, pressure maintains 4.0 × 10
-3pa, opens gas source again, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 5min, and implantation dosage is 2 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and take out material after keeping 10min in a nitrogen atmosphere, obtain blood compatibility crystalline p p sheet.
Fig. 4 is the blood compatibility polyethylene surface platelet adhesion reaction situation that embodiment 2 obtains, and obviously can find out that the crystalline p p sheet after process does not almost have platelet adhesion reaction from figure.
Embodiment 3
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.1mm by thickness, size is that the medical Polystyrene Film of 5.0cm × 10.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 1 × 10
-4pa, passes into helium, and pressure maintains 4.0 × 10
-3pa, opens gas source power supply, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 600v condition under by He isotopic geochemistry to material surface, injection length is 20min, and implantation dosage is 5 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, under helium atmosphere, keep 10min; Turn off helium and pass into ammonia, pressure maintains 4.0 × 10
-3pa, opens gas source again, acceleration voltage 2.5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 20min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under ammonia atmosphere after, obtain the Polystyrene Film of blood compatibility.
Embodiment 4
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.1mm by thickness, size is that the medical ptfe sheet material of 3.0cm × 5.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 1 × 10
-4pa, passes into helium, and pressure maintains 1.0 × 10
-2pa, opens gas source power supply, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 600v condition under by He isotopic geochemistry to material surface, injection length is 15min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under helium atmosphere; Turn off helium and pass into nitrogen and hydrogen, nitrogen and hydrogen ratio are 1:1, and pressure maintains 1.0 × 10
-3pa, opens gas source again, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 500v condition under by N~+ implantation to material surface, injection length is 10min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under nitrogen and hydrogen mixed gas atmosphere after, obtain the tetrafluoroethylene of blood compatibility.
Embodiment 5
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.01mm by thickness, size is that 5.0cm × 5.0cm medical polyvinylidene difluoride (PVDF) electrospinning film is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 2 × 10
-5pa, passes into argon gas, and pressure maintains 1.0 × 10
-2pa, opens gas source power supply, acceleration voltage 3kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 300v condition under by Ar+ion implantation to material surface, injection length is 10min, and implantation dosage is 1 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under an argon atmosphere; Turn off argon gas and pass into nitrogen and hydrogen, nitrogen and hydrogen ratio are 1:2, and pressure maintains 1.0 × 10
-3pa, opens gas source again, acceleration voltage 2kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 300v condition under by N~+ implantation to material surface, injection length is 10min, and implantation dosage is 1 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under nitrogen and hydrogen mixed gas atmosphere after, obtain the polyvinylidene difluoride (PVDF) electrospinning film of blood compatibility.
Embodiment 6
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.01mm by thickness, size is that the medical polylactic acid electrospinning film of 5.0cm × 5.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 2 × 10
-4pa, passes into argon gas, and pressure maintains 1.0 × 10
-3pa, opens gas source power supply, acceleration voltage 2kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 800v condition under by Ar+ion implantation to material surface, injection length is 30min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under argon gas atmosphere condition; Turn off argon gas and pass into ammonia and hydrogen, nitrogen and hydrogen ratio are 2:1, and pressure maintains 1.0 × 10
-3pa, opens gas source again, acceleration voltage 2kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 10min, and implantation dosage is 5 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under nitrogen and hydrogen mixed gas atmosphere after, obtain the polylactic acid electrospinning film of blood compatibility.
Embodiment 7
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.02mm by thickness, size is that 5.0cm × 5.0cm medical polycaprolactone electrospinning film is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 5 × 10
-4pa, passes into argon gas, and pressure maintains 5.0 × 10
-3pa, opens gas source power supply, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 800v condition under by Ar+ion implantation to material surface, injection length is 30min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under an argon atmosphere; Turn off argon gas and pass into nitrogen, pressure maintains 1.0 × 10
-2pa, opens gas source again, acceleration voltage 3kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 400v condition under by N~+ implantation to material surface, injection length is 5min, and implantation dosage is 1 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and take out material after keeping 10min in a nitrogen atmosphere, obtain the polycaprolactone electrospinning film of blood compatibility.
Embodiment 8
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.1mm by thickness, size is that the medical polyhydroxyalkanoate film of 5.0cm × 5.0cm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 1 × 10
-6pa, passes into helium, and pressure maintains 2.0 × 10
-3pa, opens gas source power supply, acceleration voltage 3kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 400v condition under by He isotopic geochemistry to material surface, injection length is 20min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under helium atmosphere; Turn off helium and pass into ammonia, pressure maintains 2.0 × 10
-3pa, opens gas source again, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 400v condition under by N~+ implantation to material surface, injection length is 10min, and implantation dosage is 6 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under ammonia atmosphere after, obtain the polyhydroxyalkanoate film of blood compatibility.
Embodiment 9
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.5mm by thickness, size is that 5.0cm × 5.0cm polyhydroxyalkanoate electrospinning film is positioned in the sample table in ion implantation device, source metal loads sealing equipment vacuum chamber after Ti cathode, and is evacuated down to 1 × 10
-6pa, passes into argon gas, and pressure maintains 2.0 × 10
-3pa, opens gas source power supply, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 400v condition under by Ar+ion implantation to material surface, injection length is 5min, and implantation dosage is 1 × 10
15ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under an argon atmosphere; Pressure is maintained 2.0 × 10
-3pa, opens and the source metal of Ti cathode is housed, acceleration voltage 4kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by Ti ion implantation to material surface, injection length is 1min, and implantation dosage is 1 × 10
14ions/cm
2, inject after terminating, turn off source metal power supply and argon gas is replaced by oxygen, pressure maintains 2.0 × 10
-3pa, opens gas source power supply again, acceleration voltage 4kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 600v condition under by O +ion implanted to material surface, injection length is 1min, and implantation dosage is 1 × 10
14ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under oxygen atmosphere condition after, obtain the polyhydroxyalkanoate electrospinning film of blood compatibility.
Embodiment 10
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 1.0mm by thickness, size is that the medical nylon-6 of 2.0cm × 5.0cm is positioned in the sample table in ion implantation device, source metal loads sealing equipment vacuum chamber after Ti cathode, is evacuated down to 1 × 10
-4pa, passes into helium, and pressure maintains 5.0 × 10
-3pa, opens gas source power supply, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 400v condition under by He isotopic geochemistry to material surface, injection length is 30min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under helium-atmosphere condition; Pressure is maintained 1.0 × 10
-3pa, opens and the source metal of Ti cathode is housed, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by Ti ion implantation to material surface, injection length is 18min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off source metal power supply and argon gas is replaced by oxygen, pressure maintains 2.0 × 10
-3pa, opens gas source power supply again, acceleration voltage 4kv, acceleration electric current be 1mA, arc voltage is 90v, extraction voltage be 600v condition under by O +ion implanted to material surface, injection length is 10min, and implantation dosage is 1 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under oxygen atmosphere condition after, obtain the nylon-6 of blood compatibility.
Embodiment 11
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.1mm by thickness, size is that 10.0cm × 10.0cm medical polyurethane film is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 5 × 10
-5pa, passes into argon gas, and pressure maintains 1.0 × 10
-3pa, opens gas source power supply, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 500v condition under by Ar+ion implantation to material surface, injection length is 30min, and implantation dosage is 5 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under an argon atmosphere; Turn off argon gas and pass into amine gas, pressure maintains 4.0 × 10
-3pa, opens gas source again, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 20min, and implantation dosage is 2 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under ammonia atmosphere condition after, obtain blood compatibility polyurethane film.
Embodiment 12
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 1.0mm by thickness, size is that the medical polyether-ether-ketone of 2.0cm × 5.0cm is positioned in the sample table in ion implantation device, source metal loads sealing equipment vacuum chamber after Ti cathode, is evacuated down to 1 × 10
-4pa, passes into argon gas, and pressure maintains 5.0 × 10
-3pa, opens gas source power supply, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 400v condition under by Ar+ion implantation to material surface, injection length is 30min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off gas source power supply, and keep 10min under an argon atmosphere; Pressure is maintained 1.0 × 10
-3pa, opens and the source metal of Ti cathode is housed, acceleration voltage 10kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by Ti ion implantation to material surface, injection length is 30min, and implantation dosage is 3 × 10
17ions/cm
2, inject after terminating, turn off source metal power supply and argon gas is replaced by oxygen, pressure maintains 2.0 × 10
-3pa, opens gas source power supply again, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by O +ion implanted to material surface, injection length is 15min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under oxygen atmosphere condition after, obtain the polyether-ether-ketone of blood compatibility.
Embodiment 13
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 0.5mm by diameter, long medical the gathering for 10cm be positioned in the sample table in ion implantation device to dioxy ring ethyl ketone suture line, sealing equipment vacuum chamber, is evacuated down to 5 × 10
-5pa, passes into argon gas, and pressure maintains 2.0 × 10
-3pa, opens gas source power supply, acceleration voltage 6kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 500v condition under by Ar+ion implantation to material surface, injection length is 20min, and implantation dosage is 3 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and turn off argon gas after keeping 10min under an argon atmosphere and pass into nitrogen, pressure maintains 4.0 × 10
-3pa, opens gas source again, acceleration voltage 5kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 20min, and implantation dosage is 2 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under nitrogen atmosphere condition after, obtain the poly-to dioxy ring ethyl ketone suture line of blood compatibility.
Embodiment 14
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
Be 10.0cm by diameter, the thick medical grade silicon rubber for 0.1mm is positioned in the sample table in ion implantation device, sealing equipment vacuum chamber, is evacuated down to 1 × 10
-5pa, passes into argon gas, and pressure maintains 1.0 × 10
-2pa, opens gas source power supply, acceleration voltage 3kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by Ar+ion implantation to material surface, injection length is 30min, and implantation dosage is 1 × 10
17ions/cm
2, inject after terminating, turn off gas source power supply, and turn off argon gas after keeping 10min under an argon atmosphere and pass into nitrogen, pressure maintains 1.0 × 10
-3pa, opens gas source again, acceleration voltage 3kv, acceleration electric current be 1mA, arc voltage is 70v, extraction voltage be 600v condition under by N~+ implantation to material surface, injection length is 10min, and implantation dosage is 5 × 10
16ions/cm
2, inject after terminating, turn off gas source power supply, and take out material keep 10min under nitrogen atmosphere condition after, the final silicon rubber obtaining blood compatibility.
Embodiment 15
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-2pa;
(2) rare gas element is passed into, pressure 1.0 × 10
-2pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 1.0 × 10
15ions/cm
2, injecting the degree of depth is 0.0001 μm.
Embodiment 16
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-3pa;
(2) rare gas element is passed into, pressure 1.0 × 10
-3pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 1.0 × 10
20ions/cm
2, injecting the degree of depth is 1 μm;
(3) after inert gas plasma injection terminates, pressure 1.0 × 10
-2pa, inject nitrogen plasma, implantation dosage is 0.0001ions/cm
2, injecting the degree of depth is 0.0001 μm.
Embodiment 17
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-4pa;
(2) rare gas element is passed into, pressure 5.0 × 10
-3pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 3.0 × 10
20ions/cm
2, injecting the degree of depth is 1 μm;
(3) after inert gas plasma injection terminates, pressure 1.0 × 10
-3pa, inject nitrogen plasma, implantation dosage is 1.0 × 10
18ions/cm
2, injecting the degree of depth is 1 μm;
Described nitrogen plasma is N
2and NH
3the charged ion generated.
Embodiment 18
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-4pa;
(2) rare gas element is passed into, pressure 5.0 × 10
-3pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 3.0 × 10
20ions/cm
2, injecting the degree of depth is 1 μm;
(3) after inert gas plasma injection terminates, pressure 1.0 × 10
-3pa, inject nitrogen plasma, implantation dosage is 1.0 × 10
18ions/cm
2, injecting the degree of depth is 1 μm;
Described nitrogen plasma is N
2and H
2the charged ion generated.
Embodiment 20
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-4pa;
(2) rare gas element is passed into, pressure 5.0 × 10
-3pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 3.0 × 10
20ions/cm
2, injecting the degree of depth is 1 μm;
(3) after inert gas plasma injection terminates, pressure 1.0 × 10
-2pa, Implanted Titanium plasma body, implantation dosage is 9.0 × 10
18ions/cm
2, injecting the degree of depth is 0.5 μm.
Embodiment 21
A preparation method for medical polymer material with blood compatibility, comprises the following steps:
(1) polyethylene is put into ion implantation device, be evacuated to 5.0 × 10
-4pa;
(2) rare gas element is passed into, pressure 5.0 × 10
-3pa, is injected into polyethylene surface by argon gas and helium mix plasma body, and implantation dosage is 3.0 × 10
20ions/cm
2, injecting the degree of depth is 1 μm;
(3) after inert gas plasma injection terminates, pressure 1.0 × 10
-3pa, Implanted Titanium plasma body, implantation dosage is 8.0 × 10
18ions/cm
2, injecting the degree of depth is 0.0001 μm;
(4) after the injection of titanium plasma body terminates, pressure 1.0 × 10
-2pa, continue to inject oxygen plasma, implantation dosage is 2.0 × 10
19ions/cm
2, injecting the degree of depth is 0.5 μm.
Embodiment 22
Preparation process is with embodiment 21, and unique change is that in step (4), the implantation dosage of oxygen plasma is 1.0 × 10
14ions/cm
2, injecting the degree of depth is 0.0001 μm.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (5)
1. a preparation method for medical polymer material with blood compatibility, is characterized in that, it comprises the following steps:
(1) medical macromolecular materials are put into ion implantation device, be evacuated to pressure not higher than 5.0 × 10
-2pa;
(2) pass into rare gas element, pressure is not higher than 1.0 × 10
-2pa, inert gas plasma is injected into medical macromolecular materials surface, implantation dosage is no less than 1.0 × 10
15ions/cm
2, injecting the degree of depth is 0.0001 ~ 1 μm;
(3) after inert gas plasma injection terminates, pressure is not higher than 1.0 × 10
-2pa, inject nitrogen plasma, implantation dosage is 0.0001 ~ 1.0 × 10
18ions/cm
2, injecting the degree of depth is 0.0001 ~ 1 μm;
Wherein, described rare gas element is argon gas and/or helium;
Described inert gas plasma is the charged ion that argon gas and/or helium generate.
2. the preparation method of medical polymer material with blood compatibility according to claim 1, is characterized in that, described nitrogen plasma is N
2, NH
3, N
2and H
2, NH
3and H
2, or N
2and NH
3the charged ion generated.
3. a preparation method for medical polymer material with blood compatibility, is characterized in that, it comprises the following steps:
(1) medical macromolecular materials are put into ion implantation device, be evacuated to pressure not higher than 5.0 × 10
-2pa;
(2) pass into rare gas element, pressure is not higher than 1.0 × 10
-2pa, inert gas plasma is injected into medical macromolecular materials surface, implantation dosage is no less than 1.0 × 10
15ions/cm
2, injecting the degree of depth is 0.0001 ~ 1 μm;
(3) after inert gas plasma injection terminates, pressure is not higher than 1.0 × 10
-2pa, Implanted Titanium plasma body, implantation dosage is 1.0 × 10
14~ 9.0 × 10
18ions/cm
2, injecting the degree of depth is 0.0001 ~ 0.5 μm;
Wherein, described rare gas element is argon gas and/or helium;
Described inert gas plasma is the charged ion that argon gas and/or helium generate.
4. the preparation method of medical polymer material with blood compatibility according to claim 3, it is characterized in that, the preparation method of described medical polymer material with blood compatibility also comprises: (4), after the injection of titanium plasma body terminates, pressure is not higher than 1.0 × 10
-2pa, continue to inject oxygen plasma, implantation dosage is 1.0 × 10
14~ 2.0 × 10
19ions/cm
2, injecting the degree of depth is 0.0001 ~ 0.5 μm.
5. the preparation method of the medical polymer material with blood compatibility according to claim 1 or 3, it is characterized in that, described medical macromolecular materials comprise polyethylene, polypropylene, polystyrene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly(lactic acid), polycaprolactone, polyhydroxyalkanoate, nylon, urethane, polyether-ether-ketone, gather dioxy ring ethyl ketone, silicon rubber.
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| CN105268331B (en) * | 2014-07-09 | 2018-11-09 | 天津工业大学 | A kind of preferable PVDF seperation films of blood compatibility and preparation method thereof |
| CN106084457B (en) * | 2016-06-15 | 2018-08-31 | 林泽 | A kind of medical plastic tubing and its preparation process |
| WO2019083949A2 (en) | 2017-10-27 | 2019-05-02 | Corning Incorporated | Methods of treating a surface of a polymer material by atmospheric pressure plasma |
| CN109252364B (en) * | 2018-09-19 | 2020-12-22 | 福建金成纤维制品有限公司 | Preparation method of blood-compatible polypropylene non-woven fabric |
| CN109999224B (en) * | 2019-04-17 | 2021-09-07 | 中国科学院理化技术研究所 | Antibacterial and biocompatible bone implant material and preparation method and application thereof |
| WO2020230925A1 (en) * | 2019-05-15 | 2020-11-19 | 서울대학교 산학협력단 | Method for manufacturing eptfe artificial blood vessels having improved hemocompatibility via selective plasma etching |
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