CN1454671A - Medical anticoagulant artificial material and preparing method thereof - Google Patents
Medical anticoagulant artificial material and preparing method thereof Download PDFInfo
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- CN1454671A CN1454671A CN 02116744 CN02116744A CN1454671A CN 1454671 A CN1454671 A CN 1454671A CN 02116744 CN02116744 CN 02116744 CN 02116744 A CN02116744 A CN 02116744A CN 1454671 A CN1454671 A CN 1454671A
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Abstract
The invention refers to a manmade materials for medicial anticoagulant and the manufacturing method. It solves the problem that anticoagulant problem of blood osculant materials. It is used to produce osculant blood pipe, medicinal appliance and manmade blood vessel. It comprises polyamine ester and metallic oxide nano materials. The method is that the polyamine ester is resolve in N,N-dimethylacetamide or N,N-dimethylformamide and forms the polyamine ester liquid, the metallic oxide nano materials are put into the liquid. Through high-speed mixing, shocking, and moulding, then the solvent is eliminated. The invention has good anticoagulant effect, high stretching intensity and rupture tensibility. The method and craft and the device is simple and the cost is low.
Description
(1) technical field
The present invention relates to surgery article, for example the anticoagulation of stitching thread, conduit, prosthese and blood treatment or modulation articles for use is handled, a kind of more precisely artificial material and manufacture method thereof of medical anticoagulant of and the contacted medical apparatus and instruments of blood, medical supplies and artificial organ.
(2) background technology
All and the contacted medical artificial material of biological tissue all should have excellent biological compatibility, comprise blood compatibility and histocompatibility.For the apparatus of direct intravasation, for example be used for conduit, artificial blood vessel of cardiovascular system etc.Its blood compatibility is the primary index of evaluating material performance especially.The primary index of estimating the blood compatibility of medical artificial material is the influence of this medical artificial material to blood coagulation system, that is to say the formation that whether causes blood coagulation or thrombosis.Present ideal blood compatibility material is still undiscovered.Used medical artificial material all can cause blood coagulation in various degree when contacting with blood.For example the artificial blood vessel of clinical practice at present mainly adopts polyester material or polytetrafluoroethylmaterial material to make.Because this class material can cause blood coagulation and thrombosis, thereby can only be used for larger-diameter blood vessel.And blood coagulation or thrombosis will cause angiemphraxis, and blood stasis causes the histoorgan ischemia, can jeopardize patient's life when serious.
For fear of with reduce with the blood coagulation danger that artificial material brought, in the clinical treatment of present stage, mainly be that the application heparin is as anticoagulant.Heparin is a kind of by synthetic anion mucopolysaccharide polymer in the body, can be specifically with blood plasma in Antithrombin III combine, make the formation speed of Antithrombin III increase by 1000 times, play blood coagulation resisting function.
Heparin has two kinds of application processes, and a kind of is traditional method, i.e. intravenous injection or subcutaneous injection.Another kind method is the painting method that development in recent years goes out, and is about to heparin and is coated in medical artificial material surface, in the hope of reducing the generation of blood coagulation, increases the compatibility of the blood of material.
People such as G.M.Bernacca are in the article of " Biomaterials19 (1998) 1151-1165; InVitro Blood Compatibility of Surface-Modified Polyurethanes ", introduced with polyether urethane (Polyetherurethane, PEU Estane 58315, BF Goodrich, Westerlo-Oevel, Belgium) or polyether urethane urea (Polyetherurethaneurea, PEUE, Lycra 156C Du Pont HemelHempstead, UK) make the Polyurethane pipe for raw material, again surface modification is carried out with reagent such as heparin in the surface of Polyurethane pipe and form, reduce the generation of blood clotting.
But, its weak point is arranged based on the anticoagulant of heparin.Heparin enters blood circulation, will cause bleeding tendency in the homeostasis of disturbing blood coagulation system.When patient existed blood coagulation disorders or heparin consumption to increase, bleeding tendency may be quite obvious, even produce serious consequence.Be coated in the heparin of material surface or be released into the blood, or be combined in material surface from material.The former can cause bleeding tendency, and latter Ze Keyin heparin action effect is unstable and it is of limited application.
Therefore, seeking more suitable medical anticoagulant material, to satisfy medical needs, is the developing direction of studying at present.
(3) summary of the invention
Purpose of the present invention just is to develop a kind of novel medical anticoagulant artificial material, overcomes the deficiency of medical anticoagulant artificial material in the above-mentioned prior art.
Another object of the present invention is the preparation method that works out this novel anticoagulant artificial material.
A kind of medical anticoagulant artificial material of the present invention contains the metal oxide nano-material of the Polyurethane and 0.1～30% percetage by weight of 70～99.9% percetages by weight, and the distribution of particles of metal oxide nano-material is the material that forms in Polyurethane.
Said Polyurethane is the polyester-type heat plasticity polyurethane, polyether-type heat plasticity polyurethane, polyether urethane (Polyetherurethane, PEU Estane 58315, BF Goodrich, Westerlo-Oevel, Belgium), polyether urethane urea (Polyetherurethaneurea, PEUE, Lycra 156C Du Pont HemelHempstead, UK), polycarbonate type Polyurethane a kind of Polyurethane wherein.Wherein the shore hardness of polyester-type heat plasticity polyurethane or polyether-type heat plasticity polyurethane is that 85-95A is good.
Said metal oxide nano-material is wherein a kind of of zinc oxide (ZnO) nano material, titanium dioxide (TiO2) nano material, zirconium dioxide (ZrO2) nano material, and the particle size distribution of zinc oxide, titanium dioxide, zirconium dioxide nano material is good with the 80-99% that accounts for of its granule≤50nm.
The method for making of a kind of medical anticoagulant artificial material of the present invention is:
1) presses 70-99.9% percetage by weight Polyurethane, the gold of 0.1-30% percetage by weight
Belong to the oxide-based nanomaterial batching,
2) with N,N-dimethylacetamide (Dimethylamide), N, N-dimethyl
Wherein a kind of of acetamide is solvent, is mixed with the poly-of 7-25% percetage by weight
The amine ester solution,
3) in the solution of Polyurethane, add metal oxide nano-material, carry out high-speed stirring
Mix and stir concussion, mix homogeneously,
4) will stir the Polyurethane that contains metal oxide nano-material of shaking mix homogeneously
Solution is used mould molding, removes solvent and forms medical anticoagulant artificial material.
Said Polyurethane is the polyester-type heat plasticity polyurethane, polyether-type heat plasticity polyurethane, polyether urethane (Polyetherurethane), polyether urethane urea (Polyetherurethaneurea), polycarbonate type Polyurethane a kind of Polyurethane wherein.Used raw material Polyurethane can be dissolved in can using of dimethyl acetylamide or dimethyl formamide.Certainly the medical Polyurethane that can be dissolved in dimethyl acetylamide or dimethyl formamide is better.Can also be according to the method for purification Polyurethane used in Biomaterials19 (1998) article that 1151-1165 printed, with its purification.Wherein the shore hardness of polyester-type heat plasticity polyurethane or polyether-type heat plasticity polyurethane is that 85-95A is good.
Said metal oxide nano-material is wherein a kind of of nano zinc oxide material, titanium dioxide nano material, zirconium dioxide nano material, and the particle size distribution of zinc oxide, titanium dioxide, zirconium dioxide nano material is good with the 80-99% that accounts for of its granule≤50nm.
Add metal nano material in Polyurethane solution, carry out high-speed stirred, its stir speed (S.S.) stirs 5-120 minute for well with 10000-23000 rev/min, again with 16000-20000 rev/min speed, stirs 30-90 minute for better.During concussion, shaking 1.5-6 hour, was good with 2-4 hour again.Said mould can be a glass plate, pours into the thin film that has just formed medical anticoagulant artificial material on the plate glass mould with mixing the Polyurethane solution that contains metal nano material.Form the medical anticoagulant artificial material pipe if pour on the politef pole.Certainly can also pour on the glass tubular type mould and also can form the medical anticoagulant artificial material pipe.
The mould that will have a polyurethane film at room temperature volatilized solvent 8-12 hour naturally, again in 60-80 ℃ of oven dry 10-24 hour, removed the processing of solvent and formed product.Said room temperature is 15-30 ℃.
The advantage of a kind of medical anticoagulant artificial material of the present invention and method for making thereof is: 1. the thin film of medical anticoagulant artificial material of the present invention has good blood coagulation resisting function, sees Fig. 1.2. medical anticoagulant artificial material film strength height of the present invention has high hot strength and high elongation at break.3. preparation method of the present invention, its technology, equipment are simple, are easy to grasp, and the cost of product is low, and metal oxide nano-material can scatter in thin-film material, sees Fig. 2.
Hot strength and the extension at break degree of measuring the medical anticoagulant artificial material polyurethane film of the polyurethane film do not add metal nano material and adding metal nano material of the present invention are to carry out according to the technical conditions of GB/T13541-92, under 19.7 ℃ of humitures, 17% environment, carry out with the Instron6025 stretching-machine.Each sample carries out three times to be measured, and gets its meansigma methods.
Medical anticoagulant artificial material of the present invention can be used for making the conduit of contact blood, needs the material of anticoagulant medical instruments, medical vessels and artificial blood vessel or is coated in the surface of the medical device that joins with blood.
(4) description of drawings
Fig. 1 does not contain nano zinc oxide material and contains the influence of the Polyurethane material film of not commensurability nano zinc oxide material to dynamic anticoagulant rate
Among the figure, vertical coordinate is anticoagulant rate percent %, and abscissa is that time min (branch) curve 1 is the dynamic anticoagulant rate curve that does not contain the Polyurethane material film of nano zinc oxide material.Curve 2 is the dynamic anticoagulant rate curve that contains the Polyurethane material film of 5% percetage by weight nano zinc oxide material.Curve 3 is the dynamic anticoagulant rate curve that contains the Polyurethane material film of 10% percetage by weight nano zinc oxide material.Curve 4 is the dynamic anticoagulant rate curve that contains the Polyurethane material film of 15% percetage by weight nano zinc oxide material.
Measure dynamic anti-freezing rate with BiologicalEvaluationofMedicalDevice standard test guide (chief editor Hao peace, China Standard Press, 2000) the described method of 92-93 page or leaf.
1. measure used material
1) fresh ACD human blood (1: 4)
2) calcium chloride (CaCl2) 0.2mol/L solution
3) distilled water
2. experimental procedure
1) do not contain nano zinc oxide material, contains nano zinc oxide material with above-mentioned preparation
The polyurethane film material, make it be coated in to make on the teat glass inwall and contain
0%, the Polyurethane of 5%, 10%, 15% percetage by weight nano zinc oxide material is thin
The film pipe.
2) be taken at and contain 0% percetage by weight nano zinc oxide material on the teat glass inwall
4 of Polyurethane pipes add respectively fresh ACD human blood (1: 4) in 4 arms
0.2ml after, in above-mentioned 4 arms, add again the chlorine of 0.2ml concentration 0.02mol/L
Change calcium solution, mix.
3) in the time of 5 minutes, in the first arm, add 50ml distilled water, mix,
In the second arm, add 50ml distilled water in the time of 15 minutes, mix, 30
Minute the time add 50ml distilled water at the 3rd arm, mix; At 45 minutes
Shi Zaidi four arms add 50ml distilled water, mix, and use in the 540nm wavelength
Shimadzu UV-1601 carries out spectrophotometry, and it is dynamic to calculate different time
Anti-freezing rate (percentage) provides curve 1.
4) make with above-mentioned same program and contain different amount (5%, 10%, 15%) oxygen
Change the dynamic anti-freezing rate curve 2 of zinc nano material polyurethane materials film, 3,4.
Fig. 2 contains the polyurethane materials film transmission of 5% percetage by weight nano zinc oxide material
Electronic Speculum figure.
The polyurethane film of being surveyed is for containing 95% polyether-type heat plasticity polyurethane and 5% oxygen
Change zinc nano material, in the nano zinc oxide material≤granule of 50nm accounts for 97%.Used
Projection Electronic Speculum model be the H800-800 of Hitachi, amplification: 10
5,
1mm＝10nm。
(5) specific embodiment
, can help the present invention and effect thereof are had a better understanding to medical anticoagulant artificial material of the present invention and preparation method thereof further instruction with following indefiniteness embodiment.Protection scope of the present invention is decided by claims.
Embodiment 1
The medical anticoagulant artificial material of present embodiment is made up of the 95% percetage by weight polyether-type heat plasticity polyurethane (Tianjin Polyurethane factory product) and the nano zinc oxide material of 5% percetage by weight, and the distribution of particles of nano zinc oxide material is in the polyether-type heat plasticity polyurethane and the thin-film material and the tubing that form.In the nano zinc oxide material≤Zinc oxide particles of 50nm accounts for 97%.Nano zinc oxide material is commercially available.
Its preparation method is: 1) by 95% percetage by weight polyether-type heat plasticity polyurethane, its shore hardness is the nano zinc oxide material batching of 85A and 5% percetage by weight.2) with N, N-dimethyl acetylamide (Dimethylamide) analytical pure) is configured to 7% percetage by weight polyether-type heat plasticity polyurethane solution for solvent, 3) at the N of polyether-type heat plasticity polyurethane, in the solution of N-dimethyl acetylamide, after adding nano zinc oxide material, stirred 30 minutes in 16000 rev/mins with the agitator of TURRAX T18, reuse ultrasonator (model Photoelectron Technology C 9860A) concussion 2 hours can certainly be shaken afterwards earlier and be stirred.4) the polyether-type heat plasticity polyurethane dimethylacetamide solution that contains nano zinc oxide material that shakes mix homogeneously be will stir, thin-film material and tubular material (the test tube shape material that the end is arranged, thin film test tube) made with mould with preceding method.5) mould that will have a polyether-type heat plasticity polyurethane thin film is in the volatilization 12 hours naturally of 25 ℃ of room temperatures, and oven dry 24 hours under 60 ℃ temperature again removes the solvent N,N-dimethylacetamide and forms product, makes thin film and thin film test tube.
Make polyether-type heat plasticity polyurethane thin-film material and the examination piped tubing (thin film test tube) that does not contain nano zinc oxide material with above-mentioned same method.
Carry out dynamic anticoagulant rate experiment with the thin film test tube of present embodiment and the thin film test tube that do not contain zinc oxide, the results are shown in Figure 1 curve 1, curve 2.The deployment conditions of nano zinc oxide material in film seen Fig. 2.
As can be seen from the figure the anticoagulant artificial material of present embodiment has good blood coagulation resisting function, has carried out mechanical test with said method again, the results are shown in Table 1, table 2.
Table 1 does not contain the mechanical performance of the polyether-type heat plasticity polyurethane thin-film material of nano zinc oxide material
Test number hot strength elongation at break
Mpa ％
1 35.8 360
2 35.9 404
3 38.8 390
Average 36.9 385
Table 2 contains the mechanical performance of the polyether-type heat plasticity polyurethane thin-film material of nano zinc oxide material 5% percetage by weight
Test number hot strength elongation at break
Mpa ％
1 34.7 374
2 36.0 380
3 44.3 440
Average 38.4 398
The present embodiment thin-film material is tested in the Canis familiaris L. body with tip venous thrombosis test method in the body of above-mentioned medical apparatus and instruments biological assessment standard implementation guide P94～95.Experiment shows its thin layer white thrombus of material diameter＜1mm of present embodiment, red thrombus diameter＞3mm of contrast experiment's (oxygen-free zinc (ZnO) nano material).
Embodiment 2
Its method and apparatus is substantially with embodiment 1, the material of only different is present embodiment is made up of the polyether-type heat plasticity polyurethane of 99.7% percetage by weight and the nano zinc oxide material of 0.3% percetage by weight, in the nano zinc oxide material≤and the Zinc oxide particles of 50nm accounts for 80%.Polyether-type heat plasticity polyurethane shore hardness is 95A.
Its method is that solvent for use is N, N-dimethyl acetylamide (analytical pure), be mixed with the polyether-type heat plasticity polyurethane N of 25% percetage by weight, the N-dimethylacetamide solution in 10000 rev/mins of stirrings 5 minutes, shook 1.5 hours, room temperature (15 ℃) natural evaporation solvent 8 hours, in 80 ℃ of oven dry 10 hours, its mechanical performance was average tensile strength 37.8MPa, and average elongation at break is 391%.
Its method and apparatus is substantially with embodiment 1, only different is that the medical anticoagulant artificial material material of present embodiment is made up of the polyester-type heat plasticity polyurethane (Tianjin Polyurethane factory product) and the nano zinc oxide material of 10% percetage by weight of 90% percetage by weight, in the nano zinc oxide material≤and the Zinc oxide particles of 50nm accounts for 95%.Polyester-type heat plasticity polyurethane shore hardness is 95A.
Its method is the polyester-type heat plasticity polyurethane N that is made into 20% percetage by weight, the N-dimethylacetamide solution, stirred 120 minutes in 20000 rev/mins of speed, shook 4 hours, 30 ℃ of natural evaporation solvents of room temperature 12 hours, in 70 ℃ of oven dry 18 hours, its dynamic anticoagulant rate test the results are shown in Figure 1 curve 1 and curve 3, its mechanical performance sees Table 3.Table 3 contains the mechanical performance of the polyester-type heat plasticity polyurethane thin-film material of 10% percetage by weight nano zinc oxide material
Test number hot strength elongation at break
Mpa ％
1 43.6 424
2 43.7 440
3 41.8 410
Average 43.0 425
Its method and apparatus is substantially with embodiment 3, and only different is to use the polyether-type heat plasticity polyurethane, and its experimental result and embodiment are basic identical.
Its method and apparatus is substantially with embodiment 1, only different is that the medical anticoagulant artificial material material of present embodiment is made up of the polyether-type heat plasticity polyurethane (Tianjin Polyurethane factory product) and the nano zinc oxide material of 15% percetage by weight of 85% percetage by weight, in the nano zinc oxide material≤and the Zinc oxide particles of 50nm accounts for 95%.Polyether-type heat plasticity polyurethane shore hardness is 85A.
Its method is the polyether-type heat plasticity polyurethane N that is made into 15% percetage by weight, the N-dimethylacetamide solution, stirred 60 minutes in 18000 rev/mins, shook 6 hours, 25 ℃ of natural evaporation solvents of room temperature 10 hours, in 70 ℃ of oven dry 20 hours, its dynamic anticoagulant rate test the results are shown in Figure 1 curve 1 and curve 4, its mechanical performance sees Table 4.Table 4 contains the mechanical performance of the polyether-type heat plasticity polyurethane thin-film material of 15% percetage by weight nano zinc oxide material
Test number hot strength elongation at break
Mpa ％
1 44.8 400
2 44.6 400
3 44.0 404
Average 44.4 401
Embodiment 6
Its method and apparatus is substantially with embodiment 3, the medical anticoagulant artificial material material of only different is present embodiment is made up of the polyether-type heat plasticity polyurethane of 90% percetage by weight and the titanium dioxide nano material of 10% percetage by weight, in the titanium dioxide nano material≤and the titanium dioxide granule of 50nm accounts for 97%.Polyether-type heat plasticity polyurethane shore hardness is 85A.
Its preparation method is fully with embodiment 3, and its dynamic anticoagulant rate result of the test is good.Its mechanical performance average tensile strength is 44MPa, and average elongation at break is 427%.
Embodiment 7
Its method and apparatus is substantially with embodiment 3, the medical anticoagulant artificial material material of only different is present embodiment is made up of the polyether-type heat plasticity polyurethane of 70% percetage by weight and the zirconium dioxide nano material of 30% percetage by weight, in the zirconium dioxide nano material≤and the zirconium dioxide particle of 50nm accounts for 97%.Polyether-type heat plasticity polyurethane shore hardness is 95A.
Its preparation method is fully with embodiment 3, and its dynamic anticoagulant rate result of the test is good.Its mechanical performance average tensile strength is 45MPa, and average elongation at break is 427%.
Embodiment 8
Its method and apparatus is substantially with embodiment 3, the medical anticoagulant artificial material material of only different is present embodiment is made up of the polyether urethane (Polyetherurethane) of 85% percetage by weight and the nano zinc oxide material of 15% percetage by weight, in the nano zinc oxide material≤and the Zinc oxide particles of 50nm accounts for 95%.
Its preparation method is fully with embodiment 3, and its dynamic anticoagulant rate result of the test is substantially the same manner as Example 3.Its mechanical performance is that average tensile strength is 44.6MPa, and average elongation at break is 426%.
Claims (9)
1. a medical anticoagulant artificial material is characterized in that, contains the metal oxide nano-material of the Polyurethane and 0.1～30% percetage by weight of 70～99.9% percetages by weight, and the distribution of particles of metal oxide nano-material forms material in Polyurethane.
2. according to a kind of medical anticoagulant artificial material of claim 1, it is characterized in that, said Polyurethane is the polyester-type heat plasticity polyurethane, wherein a kind of of polyether-type heat plasticity polyurethane, polyether urethane, polyether urethane urea, polycarbonate type Polyurethane.
3. according to a kind of medical anticoagulant artificial material of claim 2, it is characterized in that the shore hardness of polyester-type heat plasticity polyurethane or polyether-type heat plasticity polyurethane is 85-95A.
4. according to a kind of medical anticoagulant artificial material of claim 1, it is characterized in that said metal oxide nano-material is a kind of of zinc oxide, titanium dioxide, zirconium dioxide nano material.
5. according to a kind of medical anticoagulant artificial material of claim 4, it is characterized in that, the particle size distribution of zinc oxide, titanium dioxide, zirconium dioxide nano material, its granule≤50nm accounts for 80-99%.
6. the method for making of a medical anticoagulant artificial material, it is characterized in that, 1) presses 70-99.9% percetage by weight Polyurethane, the metal oxide nano-material batching of 0.1-30% percetage by weight, 2) with N, the N-dimethyl acetylamide, N, wherein a kind of of dinethylformamide is solvent, is mixed with the Polyurethane solution of 7-25% percetage by weight, 3) in the solution of Polyurethane, add metal oxide nano-material, carry out high-speed stirred and concussion, mix homogeneously, 4) will stir the Polyurethane solution mould molding that contains metal oxide nano-material that shakes mix homogeneously, remove the material that solvent forms.
7. according to the method for making of a kind of medical anticoagulant artificial material of claim 6, it is characterized in that stir speed (S.S.) is 10000-23000 rev/min, stirred 5-120 minute.
8. according to the method for making of a kind of medical anticoagulant artificial material of claim 6, it is characterized in that, shook 1.5-6 hour.
9. according to the method for making of a kind of medical anticoagulant artificial material of claim 6, it is characterized in that, solvent was volatilized 8-12 hour naturally, in 60-80 ℃ of oven dry 10-24 hour, remove the processing of solvent again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02116744 CN1215890C (en) | 2002-04-30 | 2002-04-30 | Medical anticoagulant artificial material and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02116744 CN1215890C (en) | 2002-04-30 | 2002-04-30 | Medical anticoagulant artificial material and preparing method thereof |
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| CN1215890C CN1215890C (en) | 2005-08-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185769B (en) * | 2007-12-10 | 2010-06-23 | 天长市天子医用科技有限公司 | Nano antimicrobial bandages |
| CN106139245A (en) * | 2016-08-17 | 2016-11-23 | 林春梅 | A kind of enhancing degradable blood vessel bracket material and preparation method thereof |
| CN106139259A (en) * | 2016-08-17 | 2016-11-23 | 林春梅 | One has drug slow release function blood vessel bracket coating and preparation method thereof |
| CN109939267A (en) * | 2019-04-04 | 2019-06-28 | 南昌大学 | A kind of antimicrobial form catheter polymer composite and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4157154A1 (en) | 2020-05-29 | 2023-04-05 | DSM IP Assets B.V. | Medical implant for cartilage replacement and method of making such implant |
| CN115667344A (en) * | 2020-05-29 | 2023-01-31 | 马斯特里赫特大学医学中心 | Polymer composition and method for manufacturing medical implant |
-
2002
- 2002-04-30 CN CN 02116744 patent/CN1215890C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185769B (en) * | 2007-12-10 | 2010-06-23 | 天长市天子医用科技有限公司 | Nano antimicrobial bandages |
| CN106139245A (en) * | 2016-08-17 | 2016-11-23 | 林春梅 | A kind of enhancing degradable blood vessel bracket material and preparation method thereof |
| CN106139259A (en) * | 2016-08-17 | 2016-11-23 | 林春梅 | One has drug slow release function blood vessel bracket coating and preparation method thereof |
| CN109939267A (en) * | 2019-04-04 | 2019-06-28 | 南昌大学 | A kind of antimicrobial form catheter polymer composite and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1215890C (en) | 2005-08-24 |
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