CN101885909A - Preparation process for polyurethane material - Google Patents
Preparation process for polyurethane material Download PDFInfo
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- CN101885909A CN101885909A CN 201010221474 CN201010221474A CN101885909A CN 101885909 A CN101885909 A CN 101885909A CN 201010221474 CN201010221474 CN 201010221474 CN 201010221474 A CN201010221474 A CN 201010221474A CN 101885909 A CN101885909 A CN 101885909A
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- polyurethane material
- urethane
- preparation technology
- polyurethane
- culture dish
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Abstract
The invention relates to a preparation process for a polyurethane material. The preparation process comprises the following process steps of: 1) adding a polyurethane raw material and poly vinyl methyl ether into a round bottomed flask; 2) adding a tetrahydrofuran organic solvent into the round bottomed flask to prepare 5 to 20 mass percent of polyurethane/poly vinyl methyl ether solution; 3) sealing and standing the solution in a fume cupboard; 4) after 2 to 4 days, pouring blend solution in the round bottomed flask into a flat bottomed culture dish; 5) sealing and standing the flat bottomed culture dish in the fume cupboard for 2 to 3 days; and 6) drying the flat bottomed culture dish in a drying box at the temperature of not higher than 60 DEG C for 24 hours to obtain a polyurethane and poly vinyl methyl ether blended thin film, namely the polyurethane material of the invention. The polyurethane material of the invention can serve as a high-end medical catheter, a guide wire or cardiovascular stents.
Description
Technical field
The invention belongs to a kind of field of medical polymer functionalizing material surface, be specifically related to a kind of preparation technology who prepares medical polyurethane materials such as high-end medical catheter, seal wire and angiocarpy bracket.
Background technology
Urethane (polyurethanes, PU) be that the basic raw material addition polymerization obtains mainly by vulcabond and dibasic alcohol or polyvalent alcohol, synthetic first by Bayer company in nineteen forty-seven, up to the present there has been the diversity of the historical .PU backbone structure of 60 years of development to determine it to have very abundant and unique physicochemical property, surface-functionalized PU has been widely used as bio-medical material. for example, get involved the polyurethane medical catheter that dispensary uses in the surgical operation at present, grafting has polyoxyethylene glycol (PEG) or heparin on the surface, play the wetting ability oilness that strengthens catheter surface, the sedimentary effect of anticoagulation and anti-protein, can be applied in the patient's blood vessel. urethane can must be to have good biocompatibility in one of application prerequisite in the surgery intervention diagnosis and therapy, comprise wetting ability, high surface lubrication, functions such as anticoagulation and proteinic deposition of prevention or absorption. and wherein the wetting ability of polyurethane surface is one of most important research contents.The damage at interface between organ and the conduit can be reduced in the PU surface that becomes lubricated in moist environment, reduces the absorption of platelet aggregation and fibrinogen, also can reduce the absorption of bacterium to material surface simultaneously.
The hydrophilic lubrication that improves polyurethane surface mainly comprises following several method: the hydrogel modification of surfaces, and polyoxyethylene (PEO) is modified, and polymethyl vinyl ether (PMVE) is modified, or the graft polymerization modification etc.The PEO modification technique is used widely at present.In the world, the high-end medical PU conduit commercialization that has functions such as the antibiotic antithrombotic of hydrophilic lubrication.But the oilness of PU material surface still can not reach requirement, and thrombocyte or absorption of proteins still exist, and the weather resistance of top coat is also not enough.Because the protection of a large amount of patents and the shortage of gordian technique; China can't produce the high-end polyurethane medical catheter material with excellent hydrophilic lubrication characteristic at present; Overseas Company is monopolizing the production technology of high-end polyurethane catheter, and high-end medical PU conduit costs an arm and a leg on the domestic market.
The aqueous solution of polymethyl vinyl ether (PMVE) has bimodal low Jie's of facing consolute temperature (LCST), therefore this class is had PMVE or MVE and other single multipolymer and the PU blend of enriching phase behavior in the aqueous solution, can greatly enrich the physicochemical property of polyurethane surface.
The contriver attempts polyurethane material and polymethyl vinyl ether material are carried out blend, and it is linked to each other with the non-bonding effect mutually, and method is simple.These new trials provide a kind of new functional polyurethane, are expected to become the material of producing high-end medical equipment.
Summary of the invention
The preparation technology who the purpose of this invention is to provide a kind of polyurethane material with urethane raw and polymethyl vinyl ether blend by a certain percentage, obtains a kind of antiplatelet adherent functional materials.
For achieving the above object, the present invention takes following processing step:
1) gets urethane raw and polymethyl vinyl ether, add in the round-bottomed flask;
2) in described round-bottomed flask, add the tetrahydrofuran (THF) organic solvent again, make mass percent and be urethane/polymethyl vinyl ether solution of 5% to 20%;
3) cover the glass cover of described round-bottomed flask, leave standstill in the stink cupboard at room temperature;
4) after 2～4 days, with in the described round-bottomed flask fully the dissolved blend solution slowly pour in the flat culture dish;
5) covering the lid of described flat culture dish, is 25 ℃-60 ℃ in room temperature range, and relative humidity was statically placed in stink cupboard 2～3 days in the environment of 20%-90%;
When 6) treating not have liquid in the described flat culture dish, place temperature not to be higher than 60 ℃ of baking ovens dry 24 hours in described flat culture dish, thereby obtain urethane and polymethyl vinyl ether blend film, be polyurethane film material of the present invention.
Further, described urethane raw comprises polyether(poly)urethane, PAUR, and the segmented copolymer of urethane.
Further, the massfraction of described urethane raw and described polymethyl vinyl ether ratio is 5: 1～25: 1.
Further, described tetrahydrofuran (THF) organic solvent also comprises methyl alcohol, ethanol, the mixture of methylene dichloride and trichloromethane or above-mentioned two or more solvents.
Further, step 2) in, described urethane raw and polymethyl vinyl ether are miscible in the tetrahydrofuran (THF) organic solvent, and the concentration of gained tetrahydrofuran solution is between 5% to 50%.
Further, the polymethyl vinyl ether step 2) combines with carbamate in the urethane with the non covalent bond combination.
Further, the preparation technology's of described polyurethane material whole film type-approval process is about a week.
Embodiment
Embodiment 1:
The preparation technology of a kind of polyurethane material of the present invention.
1) preparation urethane and poly-ethylene methacrylic ether proportioning are 15: 1 blend: under the room temperature, 0.9040g urethane (PU) and 0.0603g polymethyl vinyl ether (PVME) are added in the 50mL round-bottomed flask, in stink cupboard, add the tetrahydrofuran (THF) (THF) of 20mL and cover glass cover, left standstill three days, thing to be mixed fully dissolves.
2) preparation intermingling material film: under the room temperature, in stink cupboard, fully the dissolved blend solution is slowly poured in the flat culture dish of Φ 10cm, covers the culture dish lid, prevents that foreign matter from entering, and leaves standstill 3 days, treats that tetrahydrofuran (THF) (THF) volatilizees naturally.
3) treat obviously to observe when not having liquid in the culture dish, can see culture dish bottom tiling layer of transparent film, this film is urethane, polymethyl vinyl ether blend film.Culture dish placed be not higher than 60 ℃ of baking ovens dry 24 hours, just obtained surface of the present invention and had excellent hydrophilic and wetting ability with the controlled function polyurethane film material of proportioning, water contact angle is 48 °.
4) adopt health adult's whole blood, be collected in the centrifuge tube that contains 3.8% sodium citrate solution (blood: sodium citrate=9: 1 (V/V)), the centrifugal 10min of 800rpm, prepare be rich in thrombocyte blood plasma (Platelet-rich plasma, PRP).PC in the sample that test is obtained is about 380 * 109platelet/L.The PU/PVME sample film is activated 1d in PBS buffered soln, temperature keeps 37 ℃.Sample is immersed in the 2mL PRP blood plasma, slightly shakes 120min with shaking table, temperature still keeps 37 ℃.Take out sample and repeatedly wash, put into 2.5% glutaraldehyde PBS solution, preserve 2h down for 4 ℃ with PBS buffered soln.Then sample is clean with 37 ℃ of PBS solution cleaning downs.Be 50%, 60%, 70%, 80% with volume ratio respectively, 90%, 100% ethanol/water solution is dewatered to sample.The sample that obtains adopts lyophilize 1d, carries out the test of SEM Electronic Speculum, only finds a spot of platelet adhesion reaction thereon.
Embodiment 2:
The preparation technology of another kind of polyurethane material of the present invention.
1) preparation urethane and poly-ethylene methacrylic ether proportioning are 20: 1 blend: under the room temperature, 0.9040g urethane (PU) and 0.0470g polymethyl vinyl ether (PVME) are added in the 50mL round-bottomed flask, in stink cupboard, add the tetrahydrofuran (THF) (THF) of 20mL and cover glass cover, left standstill 3 days, thing to be mixed fully dissolves.
2) preparation intermingling material film: under the room temperature, in stink cupboard, fully the dissolved blend solution is slowly poured in the flat culture dish of Φ 10cm, covers the culture dish lid, prevents that foreign matter from entering, and leaves standstill 3 days, treats that tetrahydrofuran (THF) (THF) volatilizees naturally.
3) treat obviously to observe when not having liquid in the culture dish, can see culture dish bottom tiling layer of transparent film, this film is urethane, polymethyl vinyl ether blend film.Culture dish placed be not higher than 60 ℃ of dry 24h of baking oven, just obtained surface of the present invention and had excellent hydrophilic and wetting ability with the controlled function polyurethane film material of proportioning, water contact angle is 54 °.
4) adopt health adult's whole blood, be collected in the centrifuge tube that contains 3.8% sodium citrate solution (blood: sodium citrate=9: 1 (V/V)), the centrifugal 10min of 800rpm, prepare be rich in thrombocyte blood plasma (Platelet-rich plasma, PRP).PC in the sample that test is obtained is about 380 * 109 platelet/L.The PU/PVME sample film is activated 1d in PBS buffered soln, temperature keeps 37 ℃.Sample is immersed in the 2mL PRP blood plasma, slightly shakes 120min with shaking table, temperature still keeps 37 ℃.Take out sample and repeatedly wash, put into 2.5% glutaraldehyde PBS solution, preserve 2h down for 4 ℃ with PBS buffered soln.Then sample is clean with 37 ℃ of PBS solution cleaning downs.Be 50%, 60%, 70%, 80% with volume ratio respectively, 90%, 100% ethanol/water solution is dewatered to sample.The sample that obtains adopts lyophilize 1d, carries out the test of SEM Electronic Speculum, does not find tangible platelet adhesion reaction.
Claims (7)
1. the preparation technology of a polyurethane material is characterized in that, comprises following processing step:
1) gets urethane raw and polymethyl vinyl ether, add in the round-bottomed flask;
2) in described round-bottomed flask, add the tetrahydrofuran (THF) organic solvent again, make mass percent and be 5% to 20% urethane and polymethyl vinyl ether solution;
3) cover the glass cover of described round-bottomed flask, leave standstill in the stink cupboard at room temperature;
4) after 2～4 days, with in the described round-bottomed flask fully the dissolved blend solution slowly pour in the flat culture dish;
5) covering the lid of described flat culture dish, is 25 ℃-60 ℃ in room temperature range, and relative humidity was statically placed in stink cupboard 2～3 days in the environment of 20%-90%;
When 6) treating not have liquid in the described flat culture dish, place temperature not to be higher than 60 ℃ of baking ovens dry 24 hours in described flat culture dish, thereby obtain urethane and polymethyl vinyl ether blend film, be polyurethane film material of the present invention.
2. the preparation technology of polyurethane material according to claim 1 is characterized in that, described urethane raw comprises polyether(poly)urethane, PAUR, and the segmented copolymer of urethane.
3. the preparation technology of polyurethane material according to claim 1 is characterized in that, the massfraction ratio of described urethane raw and described polymethyl vinyl ether is 5: 1～25: 1.
4. the preparation technology of polyurethane material according to claim 1 is characterized in that, described tetrahydrofuran (THF) organic solvent also comprises methyl alcohol, ethanol, the mixture of methylene dichloride and trichloromethane or above-mentioned two or more solvents.
5. the preparation technology of polyurethane material according to claim 1 is characterized in that step 2) in, described urethane raw and polymethyl vinyl ether are miscible in the tetrahydrofuran (THF) organic solvent, and the concentration of gained tetrahydrofuran solution is between 5% to 50%.
6. the preparation technology of polyurethane material according to claim 1 is characterized in that step 2) described in polymethyl vinyl ether combine with carbamate in the urethane with the non covalent bond combination.
7. the preparation technology of polyurethane material according to claim 1 is characterized in that, the preparation technology's of described polyurethane material whole film type-approval process is a week.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102214740A CN101885909B (en) | 2010-07-08 | 2010-07-08 | Preparation process for polyurethane material |
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| CN2010102214740A CN101885909B (en) | 2010-07-08 | 2010-07-08 | Preparation process for polyurethane material |
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| CN101885909A true CN101885909A (en) | 2010-11-17 |
| CN101885909B CN101885909B (en) | 2012-01-25 |
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| CN2010102214740A Expired - Fee Related CN101885909B (en) | 2010-07-08 | 2010-07-08 | Preparation process for polyurethane material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114699563A (en) * | 2022-02-22 | 2022-07-05 | 中国医科大学附属盛京医院 | Load type polyether polyurethane film, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306605A1 (en) * | 2005-03-03 | 2009-12-10 | Kenichi Amano | Medical Treatment Device and Method for Manufacturing the Same |
| CN101612421A (en) * | 2009-07-09 | 2009-12-30 | 东南大学 | The method that has the lubricating coating of stiff stability in the medical polyurethane surface preparation |
| CN101768278A (en) * | 2010-01-19 | 2010-07-07 | 东南大学 | Method for preparing functional polyurethane material with surface modified by poly(vinyl methyl ether) |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306605A1 (en) * | 2005-03-03 | 2009-12-10 | Kenichi Amano | Medical Treatment Device and Method for Manufacturing the Same |
| CN101612421A (en) * | 2009-07-09 | 2009-12-30 | 东南大学 | The method that has the lubricating coating of stiff stability in the medical polyurethane surface preparation |
| CN101768278A (en) * | 2010-01-19 | 2010-07-07 | 东南大学 | Method for preparing functional polyurethane material with surface modified by poly(vinyl methyl ether) |
Non-Patent Citations (1)
| Title |
|---|
| 《中国组织工程研究与临床康复》 20070401 许乾慰等 脂肪族聚氨酯弹性体肝素化的血液相容性 第2415页第1栏第1行－第2418页第2栏倒数第4行 1－7 第11卷, 第13期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114699563A (en) * | 2022-02-22 | 2022-07-05 | 中国医科大学附属盛京医院 | Load type polyether polyurethane film, preparation method and application thereof |
| CN114699563B (en) * | 2022-02-22 | 2024-02-02 | 中国医科大学附属盛京医院 | Supported polyether polyurethane film, preparation method and application thereof |
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| CN101885909B (en) | 2012-01-25 |
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Granted publication date: 20120125 Termination date: 20120708 |