CN1230405A - Composite blood compatible polymer/liquid crystal film and its preparation - Google Patents
Composite blood compatible polymer/liquid crystal film and its preparation Download PDFInfo
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- CN1230405A CN1230405A CN 98122268 CN98122268A CN1230405A CN 1230405 A CN1230405 A CN 1230405A CN 98122268 CN98122268 CN 98122268 CN 98122268 A CN98122268 A CN 98122268A CN 1230405 A CN1230405 A CN 1230405A
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Abstract
The composite film consists of polymer, which is medical polyether type polyurethane, polydimethyl siloxane or polyvinyl chloride, and liquid crystal compound, which is cholesteric one or nematic one. The preparation process includes preparing solution, casting to form film, volatilizing the solvent and drying. The composite film of the present invention has anticoagulant performance meeting the requirement of human body organs and biological compatibility between the surface of film and the body tissue approaching that between body tissues. The preparation process is simple but practical.
Description
The present invention relates to blood compatibility material of bio-medical and preparation method thereof, relate in more detail with the polymer/liquid crystal composite membrane as manufacture of intraocular organ and other and the direct contacted material of blood and preparation method thereof.
The research and development of blood compatibility material are with a long history., to synthetic material, all be selected as blood compatibility material and carry out research and development to organic material from inorganic material, metal material from natural material, semisynthetic material.The blood compatibility material of clinical practice at present has medical polyurethane, medical polysiloxanes, medical polyvinyl etc.,, but all there is following shortcoming with the artificial organ of these material manufacture and other and the direct contacted material of blood:
1, the anticoagulation function gap of the anticoagulation function of material and human organ is bigger, the requirement that does not reach the human organ anticoagulation function;
2, biocompatibility between material surface and the tissue interface and the biocompatibility between the tissue differ greatly, and the degeneration, inflammation that can cause tissue thus are with pyrogenicity.
Up to the present, prior art does not also have a kind of comparatively ideal blood compatibility material.Trace it to its cause, the one, people are to the physiological environment of human body, the structure and the also inreal fully understanding of performance of histoorgan; The 2nd, people can't really grasp the structure of material and the relation between the blood compatibility so far; Do not know the interfacial phenomenon between material and the blood as yet, can't be really be according to material is carried out MOLECULE DESIGN with the structure and the pass between the blood compatibility of material.
Want to develop a kind of ideal blood compatibility material, should understand human organ, especially understand blood vessel and have fabulous blood compatibility why.Although some reason also must further be inquired into,, just can obtain a kind of comparatively ideal blood compatibility material as long as the material of design has similarity with blood vessel on configuration and performance.As everyone knows, human vas divides three layers: inner membrance, middle film and adventitia.Inner membrance is the surface that directly contacts with blood, should have fabulous blood compatibility.Although the structure of tunica intima is quite complicated, but outermost layer contains a large amount of carbohydrates to be confirmed by experiment already, this carbohydrate is in unusual suction swelling state, wherein the hydrone in hydrone and the blood is in together configuration state surely, make the interface energy between inner membrance and the blood extremely low, this is that normal blood vessels is difficult to one of major reason that takes place blood coagulation.For this reason, require synthetical this blood compatibility material to have high fluidity and easy dilatancy, but make this material of hydrone swelling in the blood, reduce the interface energy between material surface and the blood, thereby the protein adsorption that stops material surface is improved the blood compatibility of material.
The configuration that the objective of the invention is to copy tunica intima provides a kind of blood compatibility material, make the anticoagulation function of material reach the requirement of human organ anticoagulation function, and make biocompatibility between material surface and the tissue interface near the biocompatibility between the tissue.
The present invention also aims to provide a kind of preparation method of composite blood compatible polymer/liquid crystal film
The polymer/liquid crystal composite membrane is a kind of new function film that early eighties grows up, because mesomorphic low viscosity, high fluidity, easily dilatancy and order make it have many excellent properties, have shown wide application prospect at aspects such as gas separation, fluid separation applications and photoelectric display.The present invention utilizes this characteristics of polymer/liquid crystal composite membrane just, and the configuration of copying tunica intima designs polymer/liquid crystal composite membrane a kind of and blood compatibility.
Composite blood compatible polymer/liquid crystal film of the present invention is made up of polymer and liquid-crystal compounds, polymer is medical EU (being called for short PU), liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, its proportioning is L.C: PU=30: 70-60: 40 weight, and wherein L.C represents liquid-crystal compounds; Polymer can also be medical polydimethylsiloxane (being called for short DMSO), and liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, and its proportioning is L.C: DMSO=30: 70-40: 60 weight; Polymer can also be polrvinyl chloride (being called for short PVC), and liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, and its proportioning is L.C: PVC=30: 70-60: 40 weight.
Polymer used in the present invention is clinical medical polyurethane, medical polysiloxanes, medical polyvinyl as blood compatibility material,
Cholesteryl liquid crystal used in the present invention can be cholesterol oil alkenyl carbonate (being called for short COC), cholesterol diglycol carbonic ester (being called for short CDC), cholesterol triethylene-glycol carbonic ester (being called for short CTC), cholesterol tetraethylene-glycol carbonic ester (being called for short CTeC) etc.; Nematic crystal can be 4-methoxyl group benzal-4 '-n-heptyl aniline (being called for short MBHA), 4-n-pentyl-4 '-cyanobiphenyl (being called for short PNP).
Liquid crystalline type is to the influence of blood compatibility.Under the same matrix condition identical with liquid crystal content, liquid crystalline type is to the obvious effect of blood compatibility.Generally speaking, the hydrophilic cholesteryl liquid crystal is best, and non-hydrophilic cholesteryl liquid crystal takes second place, and contains the polarity gene nematic crystal and takes second place.So can reach a conclusion, under the identical condition of other condition, the hydrophilic cholesteryl liquid crystal helps improving the blood compatibility of polymeric material most.
Host material is to the influence of blood compatibility.Discussion is under the liquid crystalline type condition identical with content, and the performance of host material influences blood compatibility, and find: the blood compatibility of polysiloxane liquid/liquid-crystal composite membrane is best, but mechanical strength is poor slightly; The mechanical strength of polrvinyl chloride/liquid-crystal composite membrane is good, but blood compatibility is poor slightly; And the blood compatibility of polyurethane/liquid-crystal composite membrane and mechanical property are all good, by the skin irritation test, the Intradermal irritant test, pyrogen testing and whole body acute toxicity test show, above-mentioned all material all reveals preferable biocompatibility to organism surface, can be used as material implanted use.
Liquid crystal content in the composite membrane is more obvious to the film strength influence, as polyurethane/cholesterol oil alkenyl carbonate composite membrane, when liquid crystal content is zero, its hot strength is 16Mpa, elongation at break is 500, and when liquid crystal content reached 30%, its hot strength was 12Mpa.Elongation at break is 400.Adult's arteries axially and longitudinally breaking strength is respectively 2.4Mpa and 1.5Mpa.Elongation at break is about 200.So,, can be used as the manufacture of intraocular blood vessel from this composite membrane of mechanical strength although the adding of liquid-crystal compounds has influenced compound film strength.
The preparation method of composite blood compatible polymer/liquid crystal film of the present invention is:
1, polymer and liquid-crystal compounds are dissolved in the solvent to scale, are mixed with 3-12% solution;
2, at room temperature use framework method in glass plate or polyfluortetraethylene plate top casting film forming, under 20-50 ℃, make solvent evaporates, film forming;
3, film is put into the vacuum desiccator decompression and taken out the striping residual solvent in 5-25 hour, cancel decompression, in vacuum desiccator, make composite membrane after one week of placement.
The solvent that the present invention uses is the solvent of polymer and liquid-crystal compounds, for example oxolane, dichloroethanes, petroleum ether etc.
In film forming procedure, the concentration of polymer solution should be between 3-12% (wt), the too low difficulty or ease demoulding of concentration, and film is easily curling, and because viscosity is too big, the intermediary gas of film was difficult to volatilization, produces bubble sometimes, influences film strength when concentration was too high.
Observe from orthogonal polarizing microscope, to the composite membrane of all compositions involved in the present invention, need only liquid crystal content when 30% (wt) is above, the composite membrane surface all can form liquid crystal state, when liquid crystal content surpasses 60%, and the too poor film forming that is difficult to of composite membrane intensity.Simultaneously, also as can be seen: when liquid crystal content surpasses 30%, tangible liquid crystal phase transition absworption peak is arranged, illustrate that with this understanding liquid-crystal compounds has formed successive liquid crystalline phase (being commonly called as the liquid crystal farmland) from the thermal performance analysis result of composite membrane.
The present invention compared with prior art has following advantage:
1, composite blood compatible polymer/liquid crystal film provided by the invention, copied the configuration of tunica intima, its anticoagulation function reaches the requirement of human organ anticoagulation function substantially, in practical application with a new way of novel blood compatibility material is provided in theory.
2, the present invention imitates the configuration of blood vessel film and cell membrane, especially solid and fluid are with the characteristics of depositing a film, prepare a series of and tunica intima or the close composite membrane of membrane structure form, the biocompatibility between its surface and the tissue interface is near the biocompatibility between the tissue.
3, the hemolysis rate of composite blood compatible polymer/liquid crystal film of the present invention is 0.5-1%, well below 5% of standard-required.
4, the invention provides a kind of preparation method of composite blood compatible polymer/liquid crystal film, easy to operation.
Below by embodiment the present invention is done further narration.
Embodiment 1
The medical PU of 1.5 grams is dissolved in the purified distilled 48.5 gram tetrahydrofuran solvents, stirs and make its dissolving evenly, add 0.75 gram COC, stirred 2 hours, solution slowly is poured on clean, the aseptic polyfluortetraethylene plate, put into fume hood, at 50 ℃ of solvent flashings, film forming is inserted film in the vacuum desiccator, is decompressed to 5mmHg, dry 10 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: PU=33.3-66.7, and hemolysis rate is 0.5%.
Embodiment 2
The medical DMSO of 2.5 grams is dissolved in the purified distilled 47.5 gram petroleum ether solvents, stirs and make its dissolving evenly, add 1.2 gram MBHA, stirred 3 hours, solution slowly is poured on clean, the aseptic glass plate, put into fume hood, at 30 ℃ of solvent flashings, film forming is inserted film in the vacuum desiccator, is decompressed to 20mmHg, dry 24 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: DMSO=32.4-67.6, and hemolysis rate is 1%.
Embodiment 3
3.5 gram medical PVCs are dissolved in the purified distilled 46.5 gram dichloroethanes solvents, stir and make its dissolving evenly, add 1.6 gram CDC, stirred 2 hours, solution slowly is poured on clean, the aseptic polyfluortetraethylene plate, put into fume hood, at 40 ℃ of solvent flashings, film forming is inserted film in the vacuum desiccator, is decompressed to 10mmHg, dry 12 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: PVC=39.0-61.0, and hemolysis rate is 0.7%.
Embodiment 4
The medical PU of 2.0 grams is dissolved in the purified distilled 48.0 gram tetrahydrofuran solvents, stirs and make its dissolving evenly, add 2.0 gram CTC, stirred 3 hours, solution slowly is poured on clean, the aseptic polyfluortetraethylene plate, put into fume hood, at the 40C solvent flashing, film forming is inserted film in the vacuum desiccator, is decompressed to 10mmHg, dry 10 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: PU=50.0-50.0, and hemolysis rate is 0.7%.
Embodiment 5
The medical DMSO of 3.6 grams is dissolved in the purified distilled 46.4 gram petroleum ether solvents, stirs and make its dissolving evenly, add 2.4 gram CTeC, stirred 2 hours, solution slowly is poured on clean, the aseptic polyfluortetraethylene plate, put into fume hood, at 30 ℃ of solvent flashings, film forming is inserted film in the vacuum desiccator, is decompressed to 10mmHg, dry 5 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: DMSO=40.0-60.0, and hemolysis rate is 0.5%.。
Embodiment 6
2.5 gram medical PVCs are dissolved in the purified distilled 47.5 gram dichloroethanes solvents, stir and make its dissolving evenly, add 3.5 gram PNP, stirred 3 hours, solution slowly is poured on clean, the aseptic polyfluortetraethylene plate, put into fume hood, at 40 ℃ of solvent flashings, film forming is inserted film in the vacuum desiccator, is decompressed to 10mmHg, dry 10 hours, cancel decompression then, in vacuum desiccator, place a week, make composite blood compatible polymer/liquid crystal film of the present invention.The composite membrane proportioning is LC: PVC=58.3-41.7, and hemolysis rate is 1%.
Claims (4)
1, a kind of composite blood compatible polymer/liquid crystal film, it is characterized in that forming by polymer and liquid-crystal compounds, polymer is medical EU (being called for short PU), liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, its proportioning is L.C: PU=30: 70-60: 40 weight, wherein L.C represents liquid-crystal compounds.
2, a kind of composite blood compatible polymer/liquid crystal film, it is characterized in that forming by polymer and liquid-crystal compounds, polymer is medical polydimethylsiloxane (being called for short DMSO), liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, and its proportioning is L.C: DMSO=30: 70-40: 60 weight.
3, a kind of composite blood compatible polymer/liquid crystal film, it is characterized in that forming by polymer and liquid-crystal compounds, polymer is polrvinyl chloride (being called for short PVC), liquid-crystal compounds is cholesteric liquid crystal compound or nematic liquid crystal compound, and its proportioning is L.C: PVC=30: 70-60: 40 weight.
4, a kind of preparation method of composite blood compatible polymer/liquid crystal film is characterized in that comprising the following steps:
(1) polymer and liquid-crystal compounds are dissolved in the solvent to scale, are mixed with 3-12% solution;
(2) at room temperature use framework method in glass plate or polyfluortetraethylene plate top casting film forming, under 20-50 ℃, make solvent evaporates, film forming;
(3) film is put into the vacuum desiccator decompression and taken out the striping residual solvent in 5-25 hour, cancel decompression, in vacuum desiccator, make composite membrane after one week of placement.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98122268A CN1072021C (en) | 1998-12-31 | 1998-12-31 | Composite blood compatible polymer/liquid crystal film and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN98122268A CN1072021C (en) | 1998-12-31 | 1998-12-31 | Composite blood compatible polymer/liquid crystal film and its preparation |
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| CN1230405A true CN1230405A (en) | 1999-10-06 |
| CN1072021C CN1072021C (en) | 2001-10-03 |
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| CN98122268A Expired - Fee Related CN1072021C (en) | 1998-12-31 | 1998-12-31 | Composite blood compatible polymer/liquid crystal film and its preparation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349626C (en) * | 2005-09-29 | 2007-11-21 | 暨南大学 | Oriented polymer/liquid-crystal composite membrane blood compatibility biological material and production thereof |
| CN100446843C (en) * | 2007-02-01 | 2008-12-31 | 江南大学 | Method for preparing acrylic acid esters co-polymer membrane with anticoagulation function |
| CN102068746A (en) * | 2010-12-24 | 2011-05-25 | 重庆市科学技术研究院 | Catheter combination for cerebral blood vessel interventional therapy |
| CN103289116A (en) * | 2013-05-17 | 2013-09-11 | 暨南大学 | Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof |
| CN104582751A (en) * | 2012-06-29 | 2015-04-29 | 西托索尔本茨公司 | Methods of using polymers |
| CN109206808A (en) * | 2018-10-31 | 2019-01-15 | 西安科技大学 | A kind of preparation method of heat-conducting polymer dispersed liquid crystal film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0227299A3 (en) * | 1985-12-20 | 1987-10-07 | The Standard Oil Company | Polymer/liquid crystal composite semipermeable membranes and process for the use thereof |
-
1998
- 1998-12-31 CN CN98122268A patent/CN1072021C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349626C (en) * | 2005-09-29 | 2007-11-21 | 暨南大学 | Oriented polymer/liquid-crystal composite membrane blood compatibility biological material and production thereof |
| CN100446843C (en) * | 2007-02-01 | 2008-12-31 | 江南大学 | Method for preparing acrylic acid esters co-polymer membrane with anticoagulation function |
| CN102068746A (en) * | 2010-12-24 | 2011-05-25 | 重庆市科学技术研究院 | Catheter combination for cerebral blood vessel interventional therapy |
| CN102068746B (en) * | 2010-12-24 | 2013-04-24 | 重庆市科学技术研究院 | Catheter combination for cerebral blood vessel interventional therapy |
| CN104582751A (en) * | 2012-06-29 | 2015-04-29 | 西托索尔本茨公司 | Methods of using polymers |
| CN104582751B (en) * | 2012-06-29 | 2017-11-14 | 西托索尔本茨公司 | Use the method for polymer |
| CN103289116A (en) * | 2013-05-17 | 2013-09-11 | 暨南大学 | Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof |
| CN109206808A (en) * | 2018-10-31 | 2019-01-15 | 西安科技大学 | A kind of preparation method of heat-conducting polymer dispersed liquid crystal film |
| CN109206808B (en) * | 2018-10-31 | 2021-06-08 | 西安科技大学 | Preparation method of heat-conducting polymer liquid crystal dispersion film |
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| CN1072021C (en) | 2001-10-03 |
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