CN1215890C - Medical anticoagulant artificial material and preparing method thereof - Google Patents
Medical anticoagulant artificial material and preparing method thereof Download PDFInfo
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- CN1215890C CN1215890C CN 02116744 CN02116744A CN1215890C CN 1215890 C CN1215890 C CN 1215890C CN 02116744 CN02116744 CN 02116744 CN 02116744 A CN02116744 A CN 02116744A CN 1215890 C CN1215890 C CN 1215890C
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Abstract
The present invention relates to a medical anticoagulant artificial material and a preparation method thereof. The medical anticoagulant artificial material of the present invention is used for solving the problem of a contact blood material of anticoagulant incapability, is an artificial material for manufacturing contact blood conduit pipes, medical instruments and artificial blood vessels, and comprises polyamine ester and metal oxide nanophase materials. The preparation method of the present invention has the steps that the polyamine ester is dissolved in N, N-dimethyl acetamide or dimethyl formamide to form a polyamine ester solution, the metal oxide nanophase materials are added in the polyamine ester solution, then, high-speed stirring and vibrating are carried out, a mold is used for forming, and solvent is removed. The artificial material of the present invention has good anticoagulant effect, high tensile strength, high breaking extension, simple preparation method, process and equipment and low product cost.
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, PEUEstane58315, BF Goodrich, Westerlo-Oevel, Blegium) or polyether urethane urea (Polyetherurethaneurea, PEUE, Lycra 156C DuPont Hemel Hempstead, 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 disturb the homeostasis of blood coagulation system, causes bleeding tendency.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, contain zinc oxide, titanium dioxide, wherein a kind of metal oxide nano-material of zirconium dioxide of the Polyurethane and the 0.1-30% percetage by weight of 70-99.9% percetage by weight, the distribution of particles of metal oxide nano 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, BFGoodrich, 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 zinc oxide (ZnO) nano material, titanium dioxide (TiO
2) nano material, zirconium dioxide (ZrO
2) wherein a kind of of nano material, 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) press 70-99.9% percetage by weight Polyurethane, the metal oxide nano-material batching that the zinc oxide of 0.1-30% percetage by weight, titanium dioxide, zirconium dioxide are wherein a kind of,
2) with N,N-dimethylacetamide (Dimethylamide), wherein a kind of of N, 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 that contains metal oxide nano-material that shakes mix homogeneously, use mould molding, and remove solvent and form 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 also the Polyurethane that can be dissolved in dimethyl acetylamide or dimethyl formamide of usefulness 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 Polyurethane 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 elongation at break 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/T 13541-92, 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 surface with the contacted medical device of 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 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 anticoagulant rate with medical apparatus and instruments biological assessment 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 (CaCl
2) 0.2mol/L solution
3) distilled water
2. experimental procedure
1) do not contain nano zinc oxide material, contains the polyurethane film material of nano zinc oxide material with above-mentioned preparation, it is coated in makes the polyurethane film pipe that contains 0%, 5%, 10%, 15% percetage by weight nano zinc oxide material on the teat glass inwall.
2) be taken at 4 of Polyurethane pipes that contain 0% percetage by weight nano zinc oxide material on the teat glass inwall, after in 4 arms, adding fresh ACD human blood (1: 4) 0.2ml respectively, the calcium chloride solution that in above-mentioned 4 arms, adds 0.2ml concentration 0.02mol/L again, mix homogeneously.
3) in the time of 5 minutes, in first arm, add the 50ml distilled water, mix homogeneously, added the 50ml distilled water in the time of 15 minutes in second arm, mix homogeneously added the 50ml distilled water in the 3rd arm in the time of 30 minutes, mix homogeneously, added the 50ml distilled water at the 4th arm in the time of 45 minutes, mix homogeneously carries out spectrophotometry in the 540nm wavelength with Shimadzu UV-1601, calculate the dynamic anticoagulant rate of different time (percent), provide curve 1.
4) make with above-mentioned same degree and contain the dynamic anticoagulant rate curve 2,3,4 of not commensurability (5%, 10%, 15%) nano zinc oxide material Polyurethane material film.
Fig. 2 contains the Polyurethane material film transmission electron microscope picture of 5% percetage by weight nano zinc oxide material.
The polyurethane film of being surveyed is for containing 95% polyether-type heat plasticity polyurethane and 5% nano zinc oxide material, in the nano zinc oxide material≤and the granule of 50nm accounts for 97%.Used transmission electron microscope model is 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) be that solvent is configured to 7% percetage by weight polyether-type heat plasticity polyurethane solution with N,N-dimethylacetamide ((Dimethylamide) analytical pure).
3) at the N of polyether-type heat plasticity polyurethane, in the solution of N-dimethyl acetylamide, after adding nano zinc oxide material, agitator with TURRAX T18 stirred 30 minutes in 16000 rev/mins, 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 the polyether-type heat plasticity polyurethane thin-film material and the examination piped tubing (thin film test tube) of oxygen-free zinc nano 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 thin 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
The hot strength elongation at break
Test number
MPa ％
| 123 is average | 35.8 35.9 38.8 36.9 | 360 404 390 385 |
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
The hot strength elongation at break
Test number
MPa ％
| 123 is average | 34.7 36.0 44.3 38.4 | 374 380 440 398 |
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%.
Embodiment 3
Its method and apparatus is substantially with embodiment 1, only different is that the medical anticoagulant artificial 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, room temperature (30 ℃) natural evaporation solvent 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
The hot strength elongation at break
Test number
MPa ％
| 123 is average | 43.6 43.7 41.8 43.0 | 424 440 410 425 |
Embodiment 4
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.
Embodiment 5
Its method and apparatus is substantially with embodiment 1, only different is that the medical anticoagulant artificial 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 95% of 50nm.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, room temperature (25 ℃) natural evaporation solvent 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
The hot strength elongation at break
Test number
MPa ％
| 123 is average | 44.8 44.6 44.0 44.4 | 400 400 404 401 |
Embodiment 6
Its method and apparatus is substantially with embodiment 3, the medical anticoagulant artificial 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 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 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 average tensile strength is 44.6MPa, and average elongation at break is 426%.
Claims (8)
1 one kinds of medical anticoagulant artificial materials, it is characterized in that, contain the metal oxide nano-material that zinc oxide, titanium dioxide, the zirconium dioxide of the Polyurethane of 70～99.9% percetages by weight and 0.1～30% percetage by weight are wherein planted, the distribution of particles of metal oxide nano-material forms material in Polyurethane.
2 a kind of medical anticoagulant artificial materials according to claim 1, it is characterized in that said Polyurethane is wherein a kind of of polyester-type heat plasticity polyurethane, polyether-type heat plasticity polyurethane, polyether urethane, polyether urethane urea, polycarbonate type Polyurethane.
The 3 a kind of medical anticoagulant artificial materials according to claim 2 is characterized in that the shore hardness of polyester-type heat plasticity polyurethane or polyether-type heat plasticity polyurethane is 85-95A.
The 4 a kind of medical anticoagulant artificial materials according to claim 1 is characterized in that, the particle size distribution of zinc oxide, titanium dioxide, zirconium dioxide nano material, and its granule≤50nm accounts for 80～90%.
The method for making of 5 one kinds of medical anticoagulant artificial materials is characterized in that,
1) by 70～99.9% percetage by weight Polyurethane, the metal oxide nano-material batching that the zinc oxide of 0.1～30% percetage by weight, titanium dioxide, zirconium dioxide are wherein a kind of,
2) with N,N-dimethylacetamide, wherein a kind of of N, dinethylformamide is solvent, is mixed with the Polyurethane solution of 7～25% percetages by weight,
3) in Polyurethane solution, 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.
6 method for makings according to a kind of medical anticoagulant artificial material of claim 5 is characterized in that stir speed (S.S.) is 10000～23000 rev/mins, stir 5～120 minutes.
7 method for makings according to a kind of medical anticoagulant artificial material of claim 5 is characterized in that, shake 1.5～6 hours.
8 method for makings according to a kind of medical anticoagulant artificial material of claim 5 is characterized in that, solvent was volatilized 8～12 hours naturally, in 60～80 ℃ of oven dry 10～24 hours, remove the processing of solvent again.
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|---|---|---|---|
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Cited By (2)
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|---|---|---|---|---|
| WO2021239932A1 (en) | 2020-05-29 | 2021-12-02 | Dsm Ip Assets B.V. | Medical implant for cartilage replacement and method of making such implant |
| WO2021239931A1 (en) | 2020-05-29 | 2021-12-02 | Maastricht Universitair Medisch Centrum+ | Polymer composition and method of making a medical implant |
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| CN101185769B (en) * | 2007-12-10 | 2010-06-23 | 天长市天子医用科技有限公司 | Nano antimicrobial bandages |
| 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 |
| CN106139245A (en) * | 2016-08-17 | 2016-11-23 | 林春梅 | A kind of enhancing degradable blood vessel bracket material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021239932A1 (en) | 2020-05-29 | 2021-12-02 | Dsm Ip Assets B.V. | Medical implant for cartilage replacement and method of making such implant |
| WO2021239931A1 (en) | 2020-05-29 | 2021-12-02 | Maastricht Universitair Medisch Centrum+ | Polymer composition and method of making a medical 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 |
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