CN105288731A - Method for preparing bionic coating through crosslinking of epoxy group and mercapto group - Google Patents
Method for preparing bionic coating through crosslinking of epoxy group and mercapto group Download PDFInfo
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- CN105288731A CN105288731A CN201510784974.8A CN201510784974A CN105288731A CN 105288731 A CN105288731 A CN 105288731A CN 201510784974 A CN201510784974 A CN 201510784974A CN 105288731 A CN105288731 A CN 105288731A
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Abstract
A disclosed method for preparing bionic coating through crosslinking of epoxy group and mercapto group comprises the following steps: 1, under nitrogen protection, performing free radical polymerization reaction on a vinyl monomer containing phosphorylcholine group and a vinyl monomer containing epoxy group under effect of an initiator, so as to obtain a phosphorylcholine polymer containing epoxy; and 2, dissolving the phosphorylcholine polymer containing epoxy in a solvent, so as to obtain a polymer solution, then adding polymercaptan into the polymer solution, and mixing uniformly to obtain a mixed solution, coating the surface of a to-be-modified material by using the mixed solution, airing, then putting in distilled water for immersion processing, so as to obtain the bionic coating with an imitated cell outer-layer membrane structure on the to-be-modified material after the material is taken out. The preparation method is simple and convenient to operate, and provides a new approach for obtaining the stable coating surface possessing the imitated cell outer-layer membrane structure.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, be specifically related to a kind of epoxy radicals and sulfydryl is cross-linked the method preparing bionic coating.
Background technology
Chitosan has the advantages (CarbohydratePolymers2010,79:724-730) such as degradability, antibiotic property, nontoxic, non-stimulated, pH response, has been widely used in the fields such as biomedical.Increasing research shows: Chitosan-phospholipid complex material may be used for blood purification.Amino in chitosan molecule contributes to the absorption to toxin multiple in blood, may be used for blood Absorbent (SCI 2002,23:75-77; JournalofMicroencapsulation1993,10:475-486).Chitosan film has high dialysance, selectivity and intensity, can be used as hemodialysis material (JournalofAppliedPolymerScience1992,46:255-261; 263-269).Although Chitosan-phospholipid complex has many advantages as blood purification material, but also there is protein adsorption, platelet adhesion reaction, finally cause blood coagulation, form the problems such as thrombosis, so improve blood compatibility extremely urgent (AppliedSurfaceScience2005, the 241:485-492 of Chitosan-phospholipid complex material; Biomaterials2002,23:2561-2568; Biomaterials2003,24:3213-3220).
Phosphorylcholine (phosphorylcholine, PC) be the terminal hydrophyllic group forming cell membrane elementary cell lecithin, it is the outer functional group in the tunic of extracellular, simultaneously with positive and negative xenogenesis electric charge, there is ability and the hydrophilicity of stronger Bound moisture, the surface of this structure and composition and physiological environment interact and not only can not adsorb and depositing proteins, also can not cause platelet activation, cause the untoward reaction such as blood coagulation, have good biocompatibility.Research in recent years shows, adopts Phosphorylcholine group and polymer thereof to build at material surface and has imitating cell outer-layer membrane structure, significantly can improve the blood compatibility of material.
In recent years, grafting Phosphorylcholine micromolecular approach (CarbohydratePolymers2007,70:82-88 is adopted; Biomacromolecules2007,8:3169-3176; Biomacromolecules2006,7:3151-3156; JournalofAppliedPolymerScience2003,88:489-493; PolymerInternational2003,52:81-85; Journalofbiomaterialsscience, Polymeredition2002,13:501-510; ColloidsandSurfacesB:Biointerfaces2009,71:268-274) modification of chitosan, the blood compatibility of chitosan is significantly improved.But these modes are often not high in the density of the Phosphorylcholine group of material surface, limit its application in bio-medical material modification field and the further raising of blood compatibility.
For this reason, by the methacrylic acid containing Phosphorylcholine group-methylacryoyloxyethyl Phosphorylcholine bipolymer (PMA) polyanion, layer upon layer electrostatic self assembly is carried out with chitosan (polycation), obtain the coating surface (ColloidsandSurfacesB:Biointerfaces2011,85:48-55) with imitating cell outer-layer membrane structure.The experimental result of protein adsorption and platelet adhesion reaction shows: the blood compatibility on modified surface has had and significantly improves.In view of all advantages of this method of modifying, technical support will be provided for the blood compatibility promoting bio-medical material.But, be combined in the polymer with simulated cellulosa membrane structure coating of transplanting device surface with physical adsorption way, dissolve unavoidably in complex environment in vivo, come off.For this reason, Lewis and Xu build equality (Biomaterials2001,22:99-111; Biomaterials2004,25:3099-3108; EuropeanPolymerJournal2004,40:291-298) respectively the polymer coating containing trimethoxy silicon group and Phosphorylcholine group is studied.Result shows, in coating, on polymer molecular chain, trimethoxy silicon group chance water can be hydrolyzed, be cross-linked, and also can form covalent bond with the active group of substrate surface, thus the stability of Phosphorylcholine base polymer coating is significantly improved.As can be seen here, crosslinked between polymer and the reaction with substrate surface functional group thereof are the key factors improving Phosphorylcholine base polymer coating stability.
But, this polymer crosslinkable groups facile hydrolysis, crosslinked in building-up process, make its building-up process condition too harsh, be difficult to preserve, cause its range of application limited.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of epoxy radicals and sulfydryl to be cross-linked the method preparing bionic coating.The method is simple, easy to operate, provides a kind of new approach for obtaining the stable coating surface with imitating cell outer-layer membrane structure.The method is by being coated on chitosan film surface by the mixed solution of the phosphoryl choline polymer containing epoxy radicals and polymercaptan, the phosphoryl choline polymer of good hydrophilic property is fixed on the surface of chitosan by the reaction of epoxy radicals and chitosan surface amino groups, obtain the surface with imitating cell outer-layer membrane structure, its hydrophilic is significantly improved, and advancing angle and receding angle obviously reduce.In addition, the existence of polymercaptan cross-linking agent adds the content of chitosan surface Phosphorylcholine group, thus further increases the hydrophilic of chitosan.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the method comprises the following steps:
Step one, under nitrogen protection, carries out Raolical polymerizable by the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals, obtains the phosphoryl choline polymer containing epoxy radicals under the effect of initiator;
Step 2, obtain polymer solution by being dissolved in solvent containing the phosphoryl choline polymer of epoxy radicals described in step one, then in described polymer solution, add polymercaptan, mix homogeneously obtains mixed solution; Described mixed solution is coated on material surface to be modified, dries and to be placed in distilled water immersion treatment 5h ~ 24h under 40 DEG C ~ 90 DEG C conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure at material surface to be modified.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, vinyl monomer described in step one is methacrylic monomer, acrylic monomer, methacryl amine monomer or acrylamide monomers.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the mole of the vinyl monomer containing Phosphorylcholine group described in step one is 60% ~ 90% of the integral molar quantity of the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, vinyl monomer containing Phosphorylcholine group described in step one is methylacryoyloxyethyl Phosphorylcholine, and the vinyl monomer containing epoxy radicals is glycidyl methacrylate.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the reaction dissolvent of Raolical polymerizable described in step one is the mixed solvent of methanol and oxolane, and reaction temperature is 70 DEG C ~ 80 DEG C, and the response time is 12h ~ 24h.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the volume ratio of described methanol and oxolane is (4 ~ 6): 1.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the volume ratio of described methanol and oxolane is 5:1.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, initiator described in step one is azodiisobutyronitrile, and the mole of initiator is 0.5% ~ 1% of the integral molar quantity of the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, solvent described in step 2 is the mixed solvent of methanol and acetone, and in mixed solvent, the volumn concentration of methanol is 50% ~ 99%.
Above-mentioned a kind of epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the concentration of the phosphoryl choline polymer containing epoxy radicals in polymer solution described in step 2 is 0.2mg/mL ~ 5mg/mL, and the volume of polymercaptan is 0.25% ~ 5% of polymer solution volume.
The present invention compared with prior art has the following advantages:
1, the vinyl monomer containing Phosphorylcholine and the vinyl monomer containing epoxy radicals are passed through simple Raolical polymerizable by the present invention, the phosphoryl choline polymer of synthesis containing epoxy radicals, and itself and polymercaptan are dissolved in mixed solvent, be coated in material surface to be modified, dry and be placed on immersion treatment in distilled water, the bionic coating with imitating cell outer-layer membrane structure can be prepared, preparation method is simple, easy to operate, provides a kind of new approach for obtaining the stable coating surface with imitating cell outer-layer membrane structure.
2, the present invention is by being coated on chitosan film surface by the mixed solution of the phosphoryl choline polymer containing epoxy radicals and polymercaptan, the phosphoryl choline polymer of good hydrophilic property is fixed on the surface of chitosan by the reaction of epoxy radicals and chitosan surface amino groups, obtain the surface with imitating cell outer-layer membrane structure, its hydrophilic is significantly improved, and advancing angle and receding angle obviously reduce.In addition, the existence of polymercaptan cross-linking agent adds the content of chitosan surface Phosphorylcholine group, thus further increases the hydrophilic of chitosan.
3, bionic coating of the present invention will at blood purification, and material implanted, organizational project, the field such as medicament slow release and biosensor has broad application prospects.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
The dynamic contact angle of the bionic coating that Fig. 1 is chitosan film, prepared by comparative example 1 and bionic coating prepared by the embodiment of the present invention 1.
Fig. 2 is the dynamic contact angle test pattern of the embodiment of the present invention 1 at the bionic coating of chitosan film surface preparation.
Detailed description of the invention
Embodiment 1
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 16mmol2-methylacryoyloxyethyl Phosphorylcholine and 4mmol glycidyl methacrylate are carried out Raolical polymerizable under the effect of initiator 0.1mmol azodiisobutyronitrile, Raolical polymerizable temperature is 70 DEG C, time is 24h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 5:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 2mg step one, then in described polymer solution, add 15 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 6h under 90 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 99%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Adopt document (method of Accurate Measurement surface dynamic contact angle and influence factor, Northwest University's journal (natural science edition), Oct, 2011, Vol.41, No.5) disclosed in method measure the dynamic contact angle of bionic coating prepared by the present embodiment, the results are shown in Figure 2.In figure, the curve of labelling 1,2 and 3 is respectively first circulation, second circulation and the 3rd advancing angle circulated, all the other curves are the receding angle of three circulations, as seen from the figure, first circulation advancing angle is larger, this may be that surface hydrophilicity Phosphorylcholine group moves to coat inside, and surface hydrophobicity group is more caused.And two circulation advancing angles afterwards and receding angle overlap, and have the trend diminished along with the increase advancing angle of pendulous frequency, it is higher that this illustrates that the phosphoryl choline polymer of good hydrophilic property is fixed on the content on chitosan surface, and its hydrophilic of increase along with wetting time is significantly improved.As can be seen here, bionic coating surface prepared by the present embodiment, keeps good biocompatibility by under current intelligence in vivo.
Comparative example 1
The polymer solution of embodiment 1 is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 6h under 90 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface.
As shown in Figure 1, in figure, CS represents chitosan film, and CS-PMG represents bionic coating prepared by comparative example 1, and CS-PC-PMG represents bionic coating prepared by embodiment 1, and Ad represents advancing angle, and Re represents receding angle.As can be seen from the figure, the advancing angle of bionic coating prepared by embodiment 1 and receding angle all decrease, this is because the phosphoryl choline polymer of good hydrophilic property is fixed on the surface of chitosan by the reaction of epoxy radicals and chitosan surface amino groups, obtain the surface with imitating cell outer-layer membrane structure, its hydrophilic is significantly improved, and advancing angle and receding angle obviously reduce.In addition, the existence of polymercaptan cross-linking agent adds the hydrophilic of chitosan, and advancing angle and receding angle all reduce.This illustrates that polymercaptan adds the content of chitosan surface Phosphorylcholine group.
Embodiment 2
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 16mmol2-methylacryoyloxyethyl Phosphorylcholine and 4mmol glycidyl acrylate are carried out Raolical polymerizable under the effect of initiator 0.2mmol azodiisobutyronitrile, Raolical polymerizable temperature is 80 DEG C, time is 12h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 6:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 0.4mg step one, then in described polymer solution, add 5 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 20h under 40 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 90%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Embodiment 3
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 14mmol acrylyl oxy-ethyl Phosphorylcholine and 6mmol glycidyl acrylate are carried out Raolical polymerizable under the effect of initiator 0.1mmol azodiisobutyronitrile, Raolical polymerizable temperature is 75 DEG C, time is 20h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 4:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 10mg step one, then in described polymer solution, add 100 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 5h under 80 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 60%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Embodiment 4
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 14mmol2-Methacrylamide ethylphosphocholine and 6mmol glycidyl acrylate are carried out Raolical polymerizable under the effect of initiator 0.15mmol azodiisobutyronitrile, Raolical polymerizable temperature is 70 DEG C, time is 24h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 5:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 4mg step one, then in described polymer solution, add 60 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 10h under 70 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 50%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Embodiment 5
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 18mmol2-Methacrylamide ethylphosphocholine and 2mmol glycidyl methacrylate are carried out Raolical polymerizable under the effect of initiator 0.1mmol azodiisobutyronitrile, Raolical polymerizable temperature is 70 DEG C, time is 24h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 6:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 6mg step one, then in described polymer solution, add 80 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 10h under 60 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 80%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Embodiment 6
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 12mmol2-Methacrylamide ethylphosphocholine and 6mmol glycidyl methacrylate are carried out Raolical polymerizable under the effect of initiator 0.1mmol azodiisobutyronitrile, Raolical polymerizable temperature is 70 DEG C, time is 24h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 4:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 5mg step one, then in described polymer solution, add 40 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 24h under 50 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 99%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Embodiment 7
The present embodiment comprises the following steps:
Step one, under nitrogen protection, 12mmol2-Methacrylamide ethylphosphocholine and 6mmol glycidyl methacrylate are carried out Raolical polymerizable under the effect of initiator 0.2mmol azodiisobutyronitrile, Raolical polymerizable temperature is 70 DEG C, time is 24h, reaction terminates rear dialysis, then lyophilization at-50 DEG C, obtains the phosphoryl choline polymer containing epoxy radicals; The reaction dissolvent of described Raolical polymerizable is the mixed solvent that methanol and oxolane mix according to the volume ratio of 5:1;
Step 2, obtain 2mL polymer solution by being dissolved in the mixed solvent of methanol and acetone containing the phosphoryl choline polymer of epoxy radicals described in 3mg step one, then in described polymer solution, add 30 μ L polymercaptans, mix homogeneously obtains mixed solution; Described mixed solution is dripped and is applied to chitosan film surface, dry and be placed in distilled water, immersion treatment 12h under 75 DEG C of conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure on chitosan film surface; In the mixed solvent of described methanol and acetone, the volumn concentration of methanol is 90%.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic of the phosphoryl choline polymer containing epoxy radicals of solvent test preparation.Have no out peak at 5 ~ 7ppm place, show there is no residual monomer in gained copolymer, and successfully synthesize this polymer, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9 ~ 2.2ppm place is that the peak of methylene and pendant methyl on main chain calculates polymer composition, and known this polymer composition is basically identical with rate of charge.
Bionic coating prepared by the embodiment of the present invention 1 to embodiment 7 is compared with undressed chitosan film, and advancing angle and receding angle all decrease.This is because the phosphoryl choline polymer containing epoxy is fixed on the surface of chitosan by the reaction of epoxy radicals and chitosan surface amino groups, acquisition has the surface of imitating cell outer-layer membrane structure, and its hydrophilic is significantly improved, and advancing angle and receding angle obviously reduce.In addition, the existence of polymercaptan cross-linking agent adds the content of chitosan surface Phosphorylcholine group, and add the hydrophilic of chitosan, advancing angle and receding angle all reduce.This illustrates polymercaptan.
The above; it is only preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. epoxy radicals and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the method comprises the following steps:
Step one, under nitrogen protection, carries out Raolical polymerizable by the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals, obtains the phosphoryl choline polymer containing epoxy radicals under the effect of initiator;
Step 2, obtain polymer solution by being dissolved in solvent containing the phosphoryl choline polymer of epoxy radicals described in step one, then in described polymer solution, add polymercaptan, mix homogeneously obtains mixed solution; Described mixed solution is coated on material surface to be modified, dries and to be placed in distilled water immersion treatment 5h ~ 24h under 40 DEG C ~ 90 DEG C conditions, after taking-up, obtain the bionic coating with imitating cell outer-layer membrane structure at material surface to be modified.
2. a kind of epoxy radicals according to claim 1 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, vinyl monomer described in step one is methacrylic monomer, acrylic monomer, methacryl amine monomer or acrylamide monomers.
3. a kind of epoxy radicals according to claim 1 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the mole of the vinyl monomer containing Phosphorylcholine group described in step one is 60% ~ 90% of the integral molar quantity of the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals.
4. a kind of epoxy radicals according to claim 1 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, vinyl monomer containing Phosphorylcholine group described in step one is methylacryoyloxyethyl Phosphorylcholine, and the vinyl monomer containing epoxy radicals is glycidyl methacrylate.
5. a kind of epoxy radicals according to claim arbitrary in Claims 1-4 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the reaction dissolvent of Raolical polymerizable described in step one is the mixed solvent of methanol and oxolane, reaction temperature is 70 DEG C ~ 80 DEG C, and the response time is 12h ~ 24h.
6. a kind of epoxy radicals according to claim 5 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the volume ratio of described methanol and oxolane is (4 ~ 6): 1.
7. a kind of epoxy radicals according to claim 6 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the volume ratio of described methanol and oxolane is 5:1.
8. a kind of epoxy radicals according to claim arbitrary in Claims 1-4 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, initiator described in step one is azodiisobutyronitrile, and the mole of initiator is 0.5% ~ 1% of the integral molar quantity of the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals.
9. a kind of epoxy radicals according to claim arbitrary in Claims 1-4 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, solvent described in step 2 is the mixed solvent of methanol and acetone, and in mixed solvent, the volumn concentration of methanol is 50% ~ 99%.
10. a kind of epoxy radicals according to claim arbitrary in Claims 1-4 and sulfydryl are cross-linked the method preparing bionic coating, it is characterized in that, the concentration of the phosphoryl choline polymer containing epoxy radicals in polymer solution described in step 2 is 0.2mg/mL ~ 5mg/mL, and the volume of polymercaptan is 0.25% ~ 5% of polymer solution volume.
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| CN107652392A (en) * | 2017-10-09 | 2018-02-02 | 西安科技大学 | A kind of preparation method containing sulfydryl phosphoryl choline polymer |
| CN108517046A (en) * | 2018-04-11 | 2018-09-11 | 西安科技大学 | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl |
| CN113365674A (en) * | 2019-02-27 | 2021-09-07 | 泰尔茂株式会社 | Method for manufacturing medical instrument and medical instrument |
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| CN107652392A (en) * | 2017-10-09 | 2018-02-02 | 西安科技大学 | A kind of preparation method containing sulfydryl phosphoryl choline polymer |
| CN108517046A (en) * | 2018-04-11 | 2018-09-11 | 西安科技大学 | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl |
| CN108517046B (en) * | 2018-04-11 | 2021-01-05 | 西安科技大学 | Method for modifying chitosan membrane by using bionic coating of two phosphorylcholine polymers containing epoxy and sulfydryl |
| CN113365674A (en) * | 2019-02-27 | 2021-09-07 | 泰尔茂株式会社 | Method for manufacturing medical instrument and medical instrument |
| CN113365674B (en) * | 2019-02-27 | 2023-02-17 | 泰尔茂株式会社 | Method for manufacturing medical instrument and medical instrument |
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