CN100371033C - Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof - Google Patents
Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof Download PDFInfo
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- CN100371033C CN100371033C CNB2005101231324A CN200510123132A CN100371033C CN 100371033 C CN100371033 C CN 100371033C CN B2005101231324 A CNB2005101231324 A CN B2005101231324A CN 200510123132 A CN200510123132 A CN 200510123132A CN 100371033 C CN100371033 C CN 100371033C
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Abstract
The present invention relates to polymer/graphite oxide nanometer anticoagulating composite materials which comprise the following components with the proportion: 100 portions of polymer; 0.01 to 10 portions of graphite oxide/heparin-quaternary ammonium salt compound; 0 to 400 portions of dispersion medium; 0 to 10 portions of crosslinking agent; 0 to 1.0 portion of accelerating agent. A preparation method of the composite materials of the present invention comprises: the heparin-quaternary ammonium salt compound is used as a novel functional intercalation agent which is intercalated between every two layered graphite oxide sheet layers; a nanometer intermediate body of functional anticoagulating intercalation agent-graphite oxide is formed and is dispersed and stripped into graphite sheet layers of a nanometer level by the further intercalation reaction of the polymer, and the graphite sheet layers of a nanometer level are uniformly filled in a polymer matrix so that the polymer/graphite oxide-heparin-quaternary ammonium salt nanometer anticoagulating composite materials are obtained. The present invention can be widely used for the anticoagulation of blood containing devices (such as medical anticoagulating catheters, hemodialysis membranes, assistant circulating devices, extracorporeal blood loop connectors, blood filters, blood storing containers, blood sampling and blood transfusing appliances, etc.
Description
Technical field
The invention provides a kind of polymer/graphite oxide anticoagulant nano composite material and preparation method thereof, specially refer to a class and contain the functional type intercalator of heparin-quaternary ammonium compound and be filled into one base polymer/graphite oxide-heparin-quaternary ammonium compound anticoagulant nano composite material that forms in the polymeric matrix and preparation method thereof with the graphite oxide of this class functional type intercalator modification.
Background technology
Should have excellent biological compatibility with biological tissue contacted medical material, comprise histocompatibility, blood compatibility and mechanical compatibility.After being meant material and bio-tissue and body fluid contact, histocompatibility do not cause cell mutation, distortion, canceration and rejection.Do not cause the degeneration of plasma proteins after blood compatibility is meant material and blood contacts, do not destroy the effective ingredient of blood, do not cause the formation with thrombosis of solidifying of blood.Mechanical compatibility is to bear load for implanting, and the mechanical property that requires the biomaterial that the elastic deformation of the tissue of its elastic deformation and implant site coordinates mutually.Wherein blood compatibility (anticoagulant property) is the primary index of evaluating material performance.
The interaction of blood and bio-medical material is a very complicated process, relate to chemical constitution, surface texture, plasma protein and the hemocyte of material and the interaction of material surface, and multiple factor such as hemodynamics, also do not develop a kind of ideal blood compatibility biological material at present both at home and abroad, used medical material is when contacting with blood, the capital causes blood coagulation in various degree, and its mechanical property and blood compatibility still can not reach gratifying degree simultaneously.
Heparin is a kind of well-known anticoagulative substance, reaches anticoagulant effect by some step that stops in the blood coagulation system.Its anticlotting mechanism and anticoagulin III (AT-III claims the heparin cofactor again) are closely related.AT-III is a kind of strand glucoproteinase, can combine the generation of anticoagulant with thrombinogen.Heparin can reduce the free energy of AT-III conformation change greatly after with AT-III complexation taking place, accelerate the anticoagulation process, and speed can increase to original more than 1000 times.In the work of exploitation anticoagulant biomaterial, it is to improve one of material anticoagulation function the best way that the material surface heparinization is generally believed.But heparin is a water-soluble substances, and simply, when directly being coated in material surface, heparin can rapidly disappear under environment for use, can't stable existence in medical device surface, therefore do not have effective anticoagulant effect.
Found nano composite material that a small amount of lamellar clay and polymer monomer intercalation polymeric form by Japanese scholar since 1987 after being greatly improved on some performances, laminated nano composition just becomes the focus of people's research.Graphite can carry out similar intercalation, thereby cause people's extensive attention owing to has and the similar layer structure of clay.
But compare with clay intercalated, the intercalation of common graphite is peeled off unsatisfactory.The intercalation of montmorillonitic clay is peeled off, and mainly based on having unnecessary elecrtonegativity on its synusia, some cationic molecule between interposed layer, strut its synusia space easily.On graphite linings, then do not have this character, therefore by similar method, can't carry out intercalation, add the delocalized pi-bond and the Van der Waals force that have between the inert nature of graphite material itself and synusia thereof, realize the nano combined then more difficult of polymer/graphite by intercalation.Therefore before forming nano composite material, must carry out activation processing to graphite.Activation processing comprises two steps, the one, graphite oxidation; The 2nd, the processing that organises of functional anticoagulation intercalator.
In the graphite oxidation process, oxygen atom and carbon atom form covalent bond, the graphite lattice is increased to some extent along the c direction of principal axis,, make graphite oxide be easy to absorb polarity micromolecule (as water, ethanol etc.) and to form graphite oxide intercalation compound simultaneously because the existence of graphite layers polar group.Therefore the smooth intercalation organic compound that synthesizes of graphite oxide provides prerequisite.
The building-up process of polymer/graphite nanometer composite material is, polymer monomer (being object) is inserted in the material with layer structure, at graphite material interlayer in-situ polymerization, forms the sequential 2 D nano composite material, be the intercalation situ aggregation method, also be the embedded polymer method; In addition, polymer can also directly intercalation be compound in the graphite laminate material.The intercalation of polymer macromolecule chain can promote dissociating of graphite laminate material under a stable condition, form nanocomposite in polymeric matrix.
In preparation intercalation type nano composite material process, the selection of intercalator and use are crucial.
Anticoagulant property for heparin-quaternary ammonium compound has patent report such as US2002150670A1 both at home and abroad, JP2000288081A2, CN1448144A, but heparin-quaternary ammonium compound is inserted the graphite oxide interlayer as functional intercalator, form functional anticoagulation intercalator-graphite oxide nanostructure intermediate, and then synthetic polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite and preparation method thereof is not seen document and patent report.
In addition, the synthetic of some anticoagulant materials is that nano-powder (as metallic oxide nano powder CN1454671A, nano-sized carbon) is doped in the polymer mostly, forms " doping type macromolecule ", and nano-powder is difficult for being uniformly dispersed in polymeric film; So still needing, the dispersibility between nano-powder and polymer and the compatibility further improve.
In a word, up to now, also do not have a kind of medical anticoagulant material of modification can satisfy the high request of current cardiovascular system clinical practice fully, for example make small-caliber vascular graft, full-implantation type artificial heart etc.In addition, present most method of modifying (for example various surface graft modification) can bring certain negative effect to the mechanical property of material when improving the material blood compatibility.
Summary of the invention
In order to overcome the problem that exists in the prior art, the invention provides one base polymer/graphite oxide anticoagulant nano composite material, the present invention also will provide the preparation method of this anticoagulant material.
This kind preparation method, not only can improve the anticoagulant property of polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite, but also can improve the polymer/graphite oxide-heparin-mechanical property of quaternary ammonium salt composite and the sustained release performance of heparin, can prepare high performance polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite.
In order to finish the foregoing invention task, the invention provides a kind of polymer/graphite oxide anticoagulant nano composite material, its raw material components and weight portion content are as follows:
Graphite oxide/heparin-quaternary ammonium compound 0.01～10
Disperse medium 0～400
Cross-linking agent 0～10
Promoter 0～1.0.
The present invention can reach by following requirement:
The polymer that the present invention was suitable for is that silicone rubber (room temperature silicone rubber, high temperature silicon rubber), polyurethane or the copolymer of the two are formed; Described polymer can also be polyolefine material (PE, PVC, PP).
The functional anticoagulation intercalator that the present invention was suitable for is heparin-quaternary ammonium compound.
The quaternary ammonium salt that the present invention was suitable for is characterized in that, the chemical constitution skeleton symbol adopts the quaternary ammonium salt of following structure, and the chemical constitution skeleton symbol is R
1N
+R
2R
3R
4X
-, R wherein
1Be CH
3-; R
2Be CH
3-or C
6H
5CH
2-or-CH
2CH
2OH; R
3Be CH
3-or-CH
2CH
2OH; R
4Be chain alkyl, be selected from dodecyl, cetyl, octadecyl; X-is Cl or Br.
The graphite that the present invention was suitable for is the inorganic matter that a class has layer structure, and the carbon atom in the graphite flake layer is with SP
2Hybrid orbital and three contiguous carbon atoms form covalent bond, thereby constitute the network structure of hexaplanar, and these network structure are linked to be lamellar structure again.Interlayer relies on the such delocalized pi-bond of metalloid key to be connected with Van der Waals force, and interlamellar spacing is 0.334nm.There is a large amount of polar groups in its intergranular of graphite oxide through the graphite preparation, has specific surface area and reaches very high characteristics such as ion-exchange capacity greatly, and these characteristics have been given graphite oxide and the good intercalation compound ability of heparin-quaternary ammonium compound.Contain on the simultaneous oxidation graphite flake layer-functional groups such as OH, C=C and C-O-C, the existence of these functional groups makes graphite oxide can combine in the mode of covalent bond or ionic bond with heparin-quaternary ammonium compound.Graphite oxide can make polymer be inserted into interlayer at an easy rate after functional anticoagulation intercalator heparin-quaternary ammonium compound modification, and then forms polymer/graphite oxide anticoagulant nano material.
Described graphite oxide can make by Brodie method or Staudenmaie method or Hummer method or electrochemical oxidation process.
The used disperse medium of the present invention is alcohols, toluene, dimethylbenzene, cyclohexane extraction, dimethyl sulfoxine etc. or their mixture; The graphite oxide Dispersion of Particles that this class disperse medium can make modification evenly and carry out cation exchange reaction; And when the solwution method intercalation, graphite oxide/heparin-quaternary ammonium salt is dispersed in the polymeric matrix.
The used cross-linking agent of the present invention can be the alkyl silane of DCP or multiple functional radical, the alkoxy silane of multiple functional radical etc., as ethyl orthosilicate, silane coupler.
The used promoter of the present invention can be dibutyl tin laurate, stannous octoate or need not.
The method for preparing this polymer/graphite oxide nanocomposite is that heparin-quaternary ammonium compound as a kind of novel function intercalator, is inserted the sheet interlayer of stratiform graphite oxide; Form functional anticoagulation intercalator-Nano graphite intermediate, pass through the further intercalation of polymer again, decentralized photo is peeled off be nano level graphite flake layer, evenly be filled in the polymeric matrix, obtain polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite, the component of described composite is as follows:
Graphite oxide/heparin-quaternary ammonium compound 0.01～10
Disperse medium 0～400
Cross-linking agent 0～10
Promoter 0～1.0.
More optimize and more particularly, preparation method of the present invention is:
The operating procedure of preparation method is as follows:
With 0.01～10 part of graphite oxide, be dissolved in the NaOH solution of 2-500mL0.1M, supersound process 20min-2 hour, obtain the black colloid; Functional anticoagulation intercalator heparin sodium-quaternary ammonium compound is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 0.1～20 part, and ultrasonic 15min-30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in 100～400 parts of disperse medium for 0.01～10 part, add 100 parts of polymer, strong agitation 3～10 hours, it is fully mixed, add 0～10 part of cross-linking agent, 0～1 part of promoter is coated on the mould, places at least for 20～60 ℃ and promptly gets polymer/graphite oxide anticoagulant nano composite material in 0.2～24 hour.
Or 0.01～10 part of above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex fully mixed with 100 parts of polymer, the reuse double screw extruder promptly gets the polymer/graphite nanometer anticoagulation composite with the melt extrusion sulfidization molding.
The technology that the present invention produces polymer/graphite oxide anticoagulant nano composite material also can adopt the method for in-situ polymerization except that the method for solwution method or melt polymerization.
The invention has the beneficial effects as follows:
The present invention selects for use graphite to do matrix, and graphite is made up of pure carbon, and being used for ergonomic has excellent biological compatibility and blood compatibility, and has certain bacteriostasis.
The present invention inserts the graphite oxide interlayer with functional intercalator heparin-quaternary ammonium compound by cation exchange, form functional anticoagulation graphite oxide/heparin-quaternary ammonium salt intermediate, and graphite oxide can combine in the mode of covalent bond or ionic bond with heparin-quaternary ammonium compound, is beneficial to the macromolecular chain insertion of polymer and the formation of exfoliated anticoagulant nano composite material.
The present invention can make the graphite flake layer that has heparin-quaternary ammonium compound be evenly distributed in the polymeric matrix with nano structured unit, when heparin-quaternary ammonium compound spreads in polymeric matrix, graphite flake layer can make heparin-quaternary ammonium compound spread by straight line, force heparin-quaternary ammonium compound to take a devious route, the evolving path is increased, so the heparin rate of release slows down, sustained release performance is good, thereby obviously prolong the anticoagulation function of material; In addition, quaternary ammonium salt has certain bacteriostasis again, can make material have certain bacteriostasis again when improving the material anticoagulant property.
The present invention has solved the difficulty of nano lamellar microgranule in polymeric matrix well and has disperseed, easily reunites and the inconsistent problem in interface, the self assembly of nano lamellar microgranule is arranged and has been produced collaborative enhancing, toughening effect, so can prepare high performance polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite.This composite is because its nanostructured can be improved the anticoagulation function of polymer better, also can improve simultaneously the mechanical property of polymeric matrix, can avoid graphite directly and polymeric matrix blend and cause the problem of matrix material mechanical property deterioration.The hot strength of the mechanical property of the comparable polymer body of mechanical property of polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite can improve 83% at least, and elongation at break can improve 228% at least.
The present invention produces the technology of polymer/graphite oxide anticoagulant nano composite material, both can adopt in-situ polymerization, also can adopt the method for solution or melt polymerization, and its synthetic method is simple, and manufacturing cycle is short, is easy to industrialization.
The material of the present invention's preparation can be widely used in the anticoagulation with blood compatibility device (as medical anticoagulant conduit, hemodialysis film, auxiliary circulating equipment, extracorporeal blood circuit adapter, hemofilter, blood storage container, blood sampling blood transfusion apparatus etc.).The preparation method that is provided is simple and practical, can be used for the production of this material.
In order to be illustrated more clearly in the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.
Description of drawings
Fig. 1 is the XRD figure of Fig. 1 graphite and graphite oxide (GO);
Fig. 2 is the XRD figure of Fig. 2 GO, quaternary ammonium salt/GO, quaternary ammonium salt-heparin sodium/GO;
Fig. 3 is the XRD figure of polymer/graphite oxide anticoagulant nano composite material;
Fig. 4-1, Fig. 4-2 is respectively the SEM figure of the platelet adhesion reaction experiment of polymer, polymer/GO-quaternary ammonium salt-heparin sodium;
The specific embodiment
Embodiment 1, with reference to Fig. 1～Fig. 3, and Fig. 4-1, Fig. 4-2:
With 0.01 part of graphite oxide, be dissolved in the NaOH solution (amounting to NaOH 0.0002 part) of 2mL 0.1M, supersound process 20min obtains the black colloid; Functional anticoagulation intercalator heparin sodium-dodecane trimethyl ammonium chloride complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 0.3 part, and ultrasonic 15min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in 100 parts of disperse medium toluene for 0.01 part, add 100 parts of room temperature vulcanized silicone rubber Shens, strong agitation 3 hours, it is fully mixed, add 1 part of cross-linking agent ethyl orthosilicate, 0.1 part of promoter dibutyl tin laurate is coated on the mould, places at least for 20～60 ℃ and promptly gets polymer/graphite oxide anticoagulant nano composite material in 24 hours.
With 10 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.05 part) solution of 500mL 0.1M, supersound process 2 hours obtains the black colloid; Functional anticoagulation intercalator heparin sodium-hexadecyltrimethylammonium chloride complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 20 parts, and ultrasonic 30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in the 200 disperse medium dimethylbenzene for 10 parts, add in 100 parts of room temperature vulcanized silicone rubbers, strong agitation 6 hours, it is fully mixed, add 5 parts of anilinomethyl trimethoxy silanes, 1 part of dibutyl tin laurate is coated on the mould, places at least for 20～60 ℃ and promptly gets polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite in 24 hours.
Embodiment 3
With 2 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.006 part) solution of 60mL0.1M, supersound process 1 hour obtains the black colloid; Functional anticoagulation intercalator heparin sodium-octadecyl trimethyl ammonium chloride complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 1 part, and ultrasonic 20min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-3 parts of quaternary ammonium salt anticoagulation complex, cross-linking agent per-compound DCP are scattered under 30 ℃ in 100 parts of high-temperature silicon disulfide rubbers for 0.5 part, with the melt extrusion sulfidization molding, promptly get polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite with double screw extruder.
With 8 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.045 part) solution of 450mL0.1M, supersound process 2 hours obtains the black colloid; Functional anticoagulation intercalator heparin sodium-hexadecyltrimethylammonium chloride complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 10 parts, and ultrasonic 30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in 300 parts of disperse medium ethanol-cyclohexane extraction (1: 1) for 10 parts, add in 100 parts of room temperature vulcanized silicone rubbers, strong agitation 10 hours, it is fully mixed, add 5 parts of ethyl orthosilicates, 1 part of stannous octoate is coated on the mould, places at least for 20～60 ℃ and promptly gets polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite in 24 hours.
With 5 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.035 part) solution of 350mL 0.1M, supersound process 1 hour obtains the black colloid; Functional anticoagulation intercalator heparin sodium-trimethyl octadecyl ammonium chloride complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 8 parts, and ultrasonic 20min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-0.5 part of quaternary ammonium salt anticoagulation complex, per-compound DCP1 part are scattered under 30 ℃ in 100 parts of high-temperature silicon disulfide rubbers, with the melt extrusion sulfidization molding, promptly get polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite with double screw extruder.
With 7 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.045 part) solution of 450mL0.1M, supersound process 2 hours obtains the black colloid; Functional anticoagulation intercalator heparin sodium-octadecyl dimethyl ammonium bromide complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 10 parts, and ultrasonic 30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in 400 parts of disperse medium dimethyl sulfoxines for 7 parts, add 100 parts of polyurethane, strong agitation 5～10 hours, it is fully mixed, add 0.5 part of promoter dibutyl tin laurate, be coated on the mould, place at least for 20～60 ℃ and promptly got polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite in 24 hours.
Embodiment 7
With 9 parts of graphite oxides, be dissolved in NaOH (the amounting to NaOH 0.05 part) solution of 500mL0.1M, supersound process 2 hours obtains the black colloid; Functional anticoagulation intercalator heparin sodium-octadecyl trimethylammonium bromide complex is added in the graphite oxide colloid solution that NaOH handled under 20～60 ℃ for 9 parts, and ultrasonic 30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection and (use 0.2%AgNO less than chloride ion
3Solution detects); 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
5 parts of above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex are fully mixed with 100 parts of polyurethane, and the reuse double screw extruder promptly gets polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite with the melt extrusion molding.
Embodiment 9 is substantially with embodiment 7, and just the octadecyl trimethylammonium bromide changes stearyl dimethyl benzyl ammonium chloride into.
Embodiment 11 is substantially with embodiment 7, and just octadecyl trimethyl ammonium chloride changes methyl-2-double hydroxyethyl octadecyl ammonium into.
Embodiment 12 is substantially with embodiment 7, and just polyurethane changes polrvinyl chloride into.
Embodiment 13 is substantially with embodiment 7, and just polyurethane changes polypropylene into.
Embodiment 14 is substantially with embodiment 7, and just polyurethane changes polyethylene into.
Claims (9)
1. polymer/graphite oxide anticoagulant nano composite material, its component and weight portion content are as follows:
Polymer 100
Graphite oxide/heparin-quaternary ammonium compound 0.01～10
Disperse medium 0～400
Cross-linking agent 0～10
Promoter 0～1.0.
2. polymer/graphite oxide anticoagulant nano composite material according to claim 1 is characterized in that, described polymer is silicone rubber, polyurethane, or the two copolymer of polyurethane and silicone rubber; Or polyolefine material, silicone rubber wherein is selected from: room temperature vulcanized silicone rubber, high-temperature silicon disulfide rubber.
3. polymer/graphite oxide anticoagulant nano composite material according to claim 1 and 2 is characterized in that: described graphite oxide makes by Brodie method or Staudenmaie method or Hummer method or electrochemical oxidation process.
4. polymer/graphite oxide anticoagulant nano composite material according to claim 3 is characterized in that, adopts the quaternary ammonium salt of following structure: the chemical constitution skeleton symbol is R
1N
+R
2R
3R
4X
-, R wherein
1Be CH
3-; R
2Be CH
3-or C
6H
5CH
2-or-CH
2CH
2OH; R
3Be CH
3-or-CH
2CH
2OH; R
4Be chain alkyl, be selected from dodecyl, cetyl, octadecyl; X-is Cl or Br.
5. polymer/graphite oxide anticoagulant nano composite material according to claim 3 is characterized in that, used disperse medium is alcohols, toluene, dimethylbenzene, cyclohexane extraction, dimethyl sulfoxine, perhaps their mixture.
6. polymer/graphite oxide anticoagulant nano composite material according to claim 3 is characterized in that, wherein also contains cross-linking agent, and described cross-linking agent is the alkyl silane of peroxide DCP or multiple functional radical, the alkoxy silane of multiple functional radical.
7. according to claim 4 or 5 or 6 described polymer/graphite oxide anticoagulant nano composite materials, it is characterized in that described promoter is selected from: dibutyl tin laurate, stannous octoate.
8. the preparation method of the described polymer/graphite oxide anticoagulant nano composite material of one of claim 1～7 the steps include: heparin-quaternary ammonium compound to insert the sheet interlayer of stratiform graphite oxide as a kind of novel function intercalator; Form functional anticoagulation intercalator-graphite oxide nanostructure intermediate, pass through the further intercalation of polymer again, decentralized photo is peeled off be nano level graphite flake layer, evenly be filled in the polymeric matrix, obtain polymer/graphite oxide-heparin-quaternary ammonium salt anticoagulation composite, the component of described composite and weight portion content are as follows:
Polymer 100
Graphite oxide/heparin-quaternary ammonium compound 0.01～10
Disperse medium 0～400
Cross-linking agent 0～10
Promoter 0～1.0.
9. according to the preparation method of the described polymer/graphite oxide anticoagulant nano composite material of claim 8, it is characterized in that operating procedure is as follows:
With 0.01～10 part of graphite oxide, be dissolved in the NaOH solution of 2-500mL0.1M, supersound process 20min～2 hour obtain the black colloid; 0.01～20 part of functional anticoagulation intercalator heparin sodium-quaternary ammonium compound is described in the graphite oxide colloid solution that NaOH handled 20～60 ℃ of following addings, and ultrasonic 15min～30min obtains black precipitate; With this sedimentation and filtration, be washed with distilled water to detection less than chloride ion; 60 ℃ of following vacuum drying 24h, the black solid of gained is functional graphite oxide/heparin-quaternary ammonium salt anticoagulation complex after pulverizing;
Above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex is scattered under 20～60 ℃ in 100～400 parts of disperse medium for 0.01～10 part, add 100 parts of polymer, strong agitation 3～10 hours, it is fully mixed, add 0～10 part of cross-linking agent, 0～1 part of promoter is coated on the mould, places at least for 20～60 ℃ and promptly gets polymer/graphite oxide anticoagulant nano composite material in 0.2～24 hour;
Or 0.01～10 part of above-mentioned functions graphite oxide/heparin-quaternary ammonium salt anticoagulation complex fully mixed with 100 parts of polymer, with the melt extrusion sulfidization molding, promptly get the polymer/graphite nanometer anticoagulation composite with double screw extruder.
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| CN100413924C (en) * | 2006-11-07 | 2008-08-27 | 南京师范大学 | Polymer/montmorillonite-gallicin nano-antibacterial composite material and its preparation method |
| CN101734653B (en) * | 2008-11-04 | 2012-01-25 | 国家纳米科学中心 | Method for preparing graphite oxide-based aperture adjustable nano porous material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020150670A1 (en) * | 2001-02-09 | 2002-10-17 | Edouard Koulik | Heparin compositions and methods of making and using the same |
| CN1448144A (en) * | 2003-04-28 | 2003-10-15 | 浙江大学 | Coating liquid for improving anticoagulant performance of surface of biomedical device and coating method |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020150670A1 (en) * | 2001-02-09 | 2002-10-17 | Edouard Koulik | Heparin compositions and methods of making and using the same |
| CN1448144A (en) * | 2003-04-28 | 2003-10-15 | 浙江大学 | Coating liquid for improving anticoagulant performance of surface of biomedical device and coating method |
Non-Patent Citations (3)
| Title |
|---|
| 医用肝素化抗凝血高分子材料的研究进展. 文志红等.塑料，第34卷第2期. 2005 * |
| 氧化石墨及其聚合物纳米复合材料的研究现状. 傅玲等.炭素技术，第24卷第2期. 2005 * |
| 聚合物/石墨纳米复合材料研究进展. 陈翔峰等.高分子通报，第4期. 2004 * |
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| CN1799651A (en) | 2006-07-12 |
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