CN1554450A - Process for preparing anti-coagulant composite material of polyether urethane heparinized high molecular liquid crystal - Google Patents
Process for preparing anti-coagulant composite material of polyether urethane heparinized high molecular liquid crystal Download PDFInfo
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- CN1554450A CN1554450A CNA2003101041778A CN200310104177A CN1554450A CN 1554450 A CN1554450 A CN 1554450A CN A2003101041778 A CNA2003101041778 A CN A2003101041778A CN 200310104177 A CN200310104177 A CN 200310104177A CN 1554450 A CN1554450 A CN 1554450A
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Abstract
The present invention belongs to the field of anticoagulant material technology. The present invention prepares composite biological material with excellent anticoagulant performance through synthesizing cholest type side chain polymer liquid crystal with polyacrylamine and heparin and subsequent mixing and crosslinking with polyether urethane under certain condition. The composite material has certain cholest type side chain polymer liquid crystal content and thus excellent anticoagulant performance as well as excellent mechanical performance. The said preparation process has mild reaction condition and simple operation and is practical.
Description
One technical field the invention belongs to the anticoagulant material technical field, particularly the preparation method of anticoagulant material.
The blood compatibility of two background technology anticoagulant materials is emphasis and difficult points of medical material research, and along with going deep into of research, the poly(ether-urethane) of function admirable causes people's interest gradually.Poly(ether-urethane) is the wider macromolecular material of a class change in physical, at room temperature be easy to by liquid monomer binary or multicomponent isocyanate and binary or progressively polymerization of polyhydric alcohol, obtain from softer elastomer being widely used in the biomedical sector to multiple products such as inflexible foam plasticss.Wherein, Biomer (linear segment polyether urethaneureas) and Avcothane-51 (polydimethylsiloxane-segment polyether urethaneureas block copolymer) therefore are used widely owing to have the soft tissue compatibility preferably and blood compatibility.
Present method of modifying to poly(ether-urethane), as application number is that to adopt vulcabond be that two polyoxyethylene chains of octadecyl are bound up as coupling agent with end group for " being used to improve the composition of blood compatibility of polyurethane surface coating liquid " patented technology of 00101714, carry out the blend coating with poly(ether-urethane) then, when the solid content of coating liquid is 1～10%, can improve the anticoagulation function of composite, the realization of its anticoagulation function mainly is the coating by means of particular components.Its weak point is that this method can not effectively solve the reunification of anticoagulation function and mechanical property, and processing conditions is relatively harsh.
Three summary of the invention the purpose of this invention is to provide a kind of poly(ether-urethane) base heparinization high molecule liquid crystal anticoagulation composite preparation method, make composite have good anticoagulation function, have good mechanical mechanics property simultaneously, can solve the reunification of anticoagulation function and mechanical mechanics property effectively.This method reaction condition gentleness, equipment needed thereby is simple, and is easy to operate.
The object of the present invention is achieved like this: a kind of poly(ether-urethane) base heparinization high molecule liquid crystal anticoagulation composite preparation method, be by selecting polyacrylamide (PAM) and heparin (Heparin for use, Hep) synthesized the novel cholesteric side chain high molecule liquid crystal (SCLCP of a class, PAM-Hep), then with the poly(ether-urethane) (PEU) of itself and modification under certain condition blended cross linking prepare composite biological material with good anticoagulation function; When the mass content of cholesteric side chain high molecule liquid crystal (SCLCP) during at certain proportion, composite demonstrates good anticoagulation function, still kept simultaneously good mechanical mechanics property, having solved the reunification of anticoagulation function and mechanical mechanics property effectively, is a kind of method for preparing the anticoagulation medical composite material of practicality.
Method step of the present invention is as follows:
1 preparation high molecule liquid crystal
(1) preparation polyacrylamide (PAM) solution
At first polyacrylamide is dissolved in the distilled water and stirs, the preparation mass concentration is 0.01～1.00% PAM homogeneous solution;
(2) preparation high molecule liquid crystal
Then under 0～100 ℃ of temperature, (Heparin Hep.) is dissolved in the above-mentioned PAM homogeneous solution and stirring, prepares the novel cholesteric side chain T-shape high molecule liquid crystal (SCLCP of a class with heparin, PAM-Hep), this high molecule liquid crystal is for being the T-shape liquid crystal of side chain with the heparin.Mixing speed is 100～3000rpm when the preparation high molecule liquid crystal, and the response time is 10～300min.The mol ratio of heparin and PAM is 1: 50～1: 500 in the T-shape high molecule liquid crystal of preparation, and promptly the molar percentage of heparin is 0.002～0.02% in high molecule liquid crystal;
(3) high molecule liquid crystal is carried out the cryogenic vacuum defoaming treatment
After the reaction of (2) step finishes, the high molecule liquid crystal (SCLCP) for preparing is placed in the cryogenic vacuum, carry out the cryogenic vacuum defoaming treatment, its cryogenic temperature is-10～30 ℃, vacuum is 0.1～0.9MPa;
2 preparation composites
(1) preparation poly(ether-urethane) solution
Under 0～100 ℃ of temperature, be dissolved in the tetrahydrofuran solvent poly(ether-urethane) (PEU) and stirring, compound concentration is the poly(ether-urethane) solution of 0.002～0.02g/mL, mixing speed 100～3000rpm, the response time is 10～300min;
(2) end group activation processing
In the poly(ether-urethane) solution of (1) step preparation, add extender (as isopropyl alcohol etc.) and stir, the mass ratio of extender and poly(ether-urethane) is 0.002: 1～1: 10, the PH of regulator solution is 7～8.5 simultaneously, with the end group of priming reaction substrate molecule, forms the end group of high reaction activity.The response time of end group activation processing is 0.5～5h, and reaction temperature is 0～100 ℃, and mixing speed is 100～800rpm;
(3) activation end group grafting
In the solution after (2) step end group activation processing, add concentration and be 1.0～3.6g/10ml high reaction activity chain cross-linking agent (as succinic acid etc.) and stir, the mass ratio of chain cross-linking agent and poly(ether-urethane) is 0.0001: 1～1: 10, cross-linking agent and activation end group are reacted, its response time is 0.5～5h, mixing speed is 100～1000rpm, and reaction temperature is 0～100 ℃;
(4) with the high molecule liquid crystal blended cross linking
In the solution after (3) step activated grafting is handled, the side chain high molecule liquid crystal (SCLCP) and the stirring that add step 1 preparation, to carry out cross-linking reaction, make the poly(ether-urethane) of high molecule liquid crystal and surface grafting carry out blended cross linking and prepare composite, its response time is 0.5～10h, mixing speed is 100～1000rpm, and reaction temperature is 0～80 ℃.Side chain high molecule liquid crystal (SCLCP) is 1: 100～100: 1 with the mass ratio of poly(ether-urethane) (PEU) in the composite, and promptly the quality percentage composition of high molecule liquid crystal is 1～99% in composite;
(5) composite film forming
To carry out the reacted composite solution of blended cross linking through (4) step and pour casting film-forming in the mould into, and after natural air drying extremely solidifies substantially, put into the baking oven cold drying again and become the composite finished product film, its cryogenic temperature is 0～40 ℃;
(6) subsequent treatment
At last the composite finished product film is placed distilled water to soak, wash to neutrality, freeze-day with constant temperature is promptly made poly(ether-urethane) base heparinization high molecule liquid crystal anticoagulation medical composite material to constant weight again.
The anticoagulation composite of the present invention's preparation, be heparin to be dissolved in making high molecule liquid crystal in the polyacrylamide solution earlier, and then with high molecule liquid crystal and poly(ether-urethane) blended cross linking synthetic composite material, and the quality percentage composition of high molecule liquid crystal is 1～99% in the composite, and have aqueous favoring with hydrophobic with the equally distributed surface microstructure of nano-scale, thereby this composite has good anticoagulation function, simultaneously still keep good mechanical mechanics property, solved the reunification of the anticoagulation function and the mechanical mechanics property of composite effectively.The inventive method reaction condition gentleness, equipment needed thereby is simple, and is easy to operate, is a kind of effective ways of simple, convenient, practical preparation anticoagulation medical composite material.
Four specific embodiment further specify the present invention below in conjunction with instantiation:
Embodiment one: the liquid crystal mass content is the preparation method of 10% composite:
1, the preparation method of cholesteric high molecule liquid crystal:
(1) takes by weighing that to tire be that the heparin 0.257g of 100～140u/mg is dissolved in the 25ml distilled water, shaking table vibration, fully dissolving;
(2) take by weighing polymer molecular weight 2,000, the polyacrylamide 0.260g more than 000 is dissolved in the 25ml distilled water, and solution is transparent thick;
(3) under the effect of stirring at low speed, slowly dripping concentration in polyacrylamide solution is the aqueous solution of 0.257g/25ml heparin, and speed is dripped in control, controls temperature simultaneously at 36～38 ℃, PH=4.7;
(4) reaction finishes, and after normal pressure or vacuum (0.5Mpa) discontinuous degassing is handled, keeps in Dark Place under 0 ℃.
2, the preparation method of composite:
(1) accurately takes by weighing poly(ether-urethane) (PEU) 0.505g and be dissolved in the 5ml tetrahydrofuran solvent heating for dissolving;
(2) in above-mentioned solution, add the 0.1ml isopropyl alcohol and make extender, carry out the end group activation processing under the alkaline environment (pH=8);
(3) dripping the 1ml mass concentration in the solution after the end group activation processing is the succinic acid aqueous solution cross-linking agent of 0.9g/ml, crosslinked with PEU surface active end group carboxylic splice grafting branch;
(4) the control stir speed (S.S.) is 300rpm, adds the previously prepared high molecule liquid crystal of 0.056g, carries out the blended cross linking reaction under the effect of cross-linking agent;
(5) after step (4) finishes, push film forming on the clean level and smooth mould, lucifuge shady and cool place natural air drying or low temperature (30 ℃) oven drying;
(6) desciccator diaphragm reuse distilled water immersion, flushing are taken out and are dried to constant weight to neutral.
Embodiment two: the liquid crystal mass content is the preparation method of 15% composite:
1, the preparation method of cholesteric high molecule liquid crystal is with embodiment one;
2, the preparation method of composite is with embodiment one, but the addition of high molecule liquid crystal is 0.089g in the step (4), and all the other operations are identical with embodiment one.
Embodiment three: the liquid crystal mass content is the preparation method of 20% composite:
1, the preparation method of cholesteric high molecule liquid crystal is with embodiment one;
2, the preparation method of composite is with embodiment one, but the addition of high molecule liquid crystal is 0.126g in the step (4), and all the other operations are identical with embodiment one.
Embodiment four: the liquid crystal mass content is the preparation method of 25% composite:
1, the preparation method of cholesteric high molecule liquid crystal is with embodiment one;
2, the preparation method of composite is with embodiment one, but the addition of high molecule liquid crystal is 0.168g in the step (4), and all the other operations are identical with embodiment one.
Claims (3)
1, a kind of polyetheramine ester group heparinization high molecule liquid crystal anticoagulation composite preparation method is characterized in that its method step is as follows:
(1) preparation high molecule liquid crystal
1. prepare polyacrylamide solution
At first polyacrylamide is dissolved in the distilled water, the preparation mass percent is 0.01～1.00% polyacrylamide homogeneous solution;
2. prepare high molecule liquid crystal
Under 0～100 ℃ of temperature, be dissolved in the polyacrylamide homogeneous solution heparin and stirring, wherein the mol ratio of heparin and polyacrylamide is 1: 50～1: 500;
3. high molecule liquid crystal is carried out the cryogenic vacuum defoaming treatment
The after 2. the step reaction finishes, the high molecule liquid crystal of preparing is placed in the cryogenic vacuum, carry out the vacuum defoaming treatment.
(2) preparation composite
1. prepare poly(ether-urethane) solution
Under 0～100 ℃ of temperature, be dissolved in the tetrahydrofuran solvent poly(ether-urethane) and stirring, compound concentration is the poly(ether-urethane) solution of 0.002～0.02g/mL;
2. end group activation processing
1. add extender in the poly(ether-urethane) solution of step preparation and stir the, regulating its pH value simultaneously is 7～8.5;
3. activate the end group grafting
2. to add concentration in the solution of step after handling be 1.0～3.6g/10ml chain cross-linking agent and stir the;
4. with the high molecule liquid crystal blended cross linking
In the solution that 3. goes on foot after grafting is handled, add the side chain high molecule liquid crystal of step (1) preparation and stir, the mass ratio of its high molecule liquid crystal and poly(ether-urethane) is 1: 100～100: 1;
5. composite film forming
To 4. go on foot reacted composite solution through the and pour casting film-forming in the mould into, natural air drying is put into baking oven cold drying film forming after solidify substantially again;
6. subsequent treatment
Place distilled water to soak, wash to neutrality the film finished product at last, freeze-day with constant temperature is to constant weight again.
2, according to the described polyetheramine ester group of claim 1 heparinization high molecule liquid crystal anticoagulation composite preparation method, the mixing speed that it is characterized in that described preparation high molecule liquid crystal is 100～3000rpm, response time is that the temperature of the described high molecule liquid crystal of 10～300min when carrying out the low temperature defoaming treatment is-10～30 ℃, and vacuum is 0.1～0.9Mpa; Described poly(ether-urethane) is dissolved in the tetrahydrofuran solvent and the mixing speed that stirs is 100～3000rpm, and the response time is 10～300min; The described response time of carrying out the end group activation processing is 0.5～5h, and reaction temperature is 0～100 ℃, and mixing speed is 100～800rpm; The response time of described activation end group graft reaction is 0.5～5h, and reaction temperature is 0～100 ℃, and mixing speed is 100～1000rpm; The response time that described and high molecule liquid crystal carries out the blended cross linking reaction is 0.5～10h, and mixing speed is 100～1000rpm, and reaction temperature is 0～80 ℃; The temperature that described composite material film carries out oven drying at low temperature is 0～40 ℃.
3, according to claim 1,2 described polyetheramine ester group heparinization high molecule liquid crystal anticoagulation composite preparation methoies, it is characterized in that described high molecule liquid crystal is the T-shape liquid crystal of heparin as side chain; Described extender is an isopropyl alcohol; Described chain cross-linking agent is a succinic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310104177 CN1256991C (en) | 2003-12-27 | 2003-12-27 | Process for preparing anti-coagulant composite material of polyether urethane heparinized high molecular liquid crystal |
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| CN 200310104177 CN1256991C (en) | 2003-12-27 | 2003-12-27 | Process for preparing anti-coagulant composite material of polyether urethane heparinized high molecular liquid crystal |
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| CN1554450A true CN1554450A (en) | 2004-12-15 |
| CN1256991C CN1256991C (en) | 2006-05-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446843C (en) * | 2007-02-01 | 2008-12-31 | 江南大学 | Method for preparing acrylic acid esters co-polymer membrane with anticoagulation function |
| CN101265112B (en) * | 2008-04-17 | 2011-08-31 | 上海伊索热能技术有限公司 | Suspending agent of mica mineral in water solution |
| CN102695530A (en) * | 2009-09-17 | 2012-09-26 | 戈尔企业控股股份有限公司 | Novel heparin entities and methods of use |
-
2003
- 2003-12-27 CN CN 200310104177 patent/CN1256991C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446843C (en) * | 2007-02-01 | 2008-12-31 | 江南大学 | Method for preparing acrylic acid esters co-polymer membrane with anticoagulation function |
| CN101265112B (en) * | 2008-04-17 | 2011-08-31 | 上海伊索热能技术有限公司 | Suspending agent of mica mineral in water solution |
| CN102695530A (en) * | 2009-09-17 | 2012-09-26 | 戈尔企业控股股份有限公司 | Novel heparin entities and methods of use |
| CN102695530B (en) * | 2009-09-17 | 2018-11-30 | W.L.戈尔及同仁股份有限公司 | Novel heparin entity and its application method |
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| Publication number | Publication date |
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| CN1256991C (en) | 2006-05-24 |
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