CN105288731B - A kind of method that epoxy radicals prepares bionic coating with sulfydryl crosslinking - Google Patents
A kind of method that epoxy radicals prepares bionic coating with sulfydryl crosslinking Download PDFInfo
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- CN105288731B CN105288731B CN201510784974.8A CN201510784974A CN105288731B CN 105288731 B CN105288731 B CN 105288731B CN 201510784974 A CN201510784974 A CN 201510784974A CN 105288731 B CN105288731 B CN 105288731B
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Abstract
The invention discloses a kind of method that epoxy radicals and sulfydryl crosslinking prepare bionic coating, comprise the following steps：First, under nitrogen protection, the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxy radicals are subjected to Raolical polymerizable in the presence of initiator, obtain the phosphoryl choline polymer containing epoxy radicals；2nd, the phosphoryl choline polymer containing epoxy radicals is dissolved in solvent and obtains polymer solution, then add polymercaptan into the polymer solution, it is well mixed to obtain mixed solution；The mixed solution is coated on material surface to be modified, immersion treatment in distilled water is placed in after drying, the bionic coating with imitating cell outer-layer membrane structure is obtained in material surface to be modified after taking-up.Preparation method of the present invention is simple and convenient to operate, and the coating surface with imitating cell outer-layer membrane structure to obtain stable provides a kind of new approach.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to a kind of epoxy radicals
The method that bionic coating is prepared with sulfydryl crosslinking.
Background technology
Chitosan has the advantages that degradability, antibiotic property, nontoxic, non-stimulated, pH responses (Carbohydrate
Polymers 2010,79:724-730), it has been widely used in the fields such as biomedicine.Increasing research shows：
Chitosan-phospholipid complex material can be used for blood purification.Amino in chitosan molecule contributes to a variety of toxin in blood
Absorption, can be used for blood Absorbent (SCI 2002,23:75-77；Journal of
Microencapsulation 1993,10:475-486).Chitosan film has high dialysance, selectivity and intensity, can be with
As haemodialysis material (Journal of Applied Polymer Science 1992,46:255-261；263-269).
Although Chitosan-phospholipid complex has many advantages as blood purification material, there is also protein absorption, blood is small
Plate sticks, and ultimately results in blood coagulation, the problems such as forming thrombus, so the blood compatibility for improving Chitosan-phospholipid complex material is compeled
In the eyebrows and eyelashes (Applied Surface Science 2005,241:485-492；Biomaterials 2002,23:2561-
2568；Biomaterials 2003,24:3213-3220).
Phosphorylcholine (phosphorylcholine, PC) is the terminal hydrophyllic group for forming cell membrane elementary cell lecithin, is
Outer layer functional group in extracellular tunic, simultaneous with positive and negative xenogenesis electric charge, ability and hydrophily with stronger combination water
Can, the surface of this structure and composition will not only be adsorbed with physiological environment interaction and depositing proteins, will not also trigger
Platelet activation, cause the adverse reactions such as blood coagulation, there is good biocompatibility.Research in recent years shows, using phosphinylidyne
Choline group and its polymer have imitating cell outer-layer membrane structure in material surface structure, can significantly improve the blood phase of material
Capacitive.
In recent years, using approach (the Carbohydrate Polymers 2007,70 of grafting Phosphorylcholine small molecule:82-
88；Biomacromolecules 2007,8:3169-3176；Biomacromolecules 2006,7:3151-3156；
Journal of Applied Polymer Science 2003,88:489-493；Polymer International
2003,52:81-85；Journal of biomaterials science,Polymer edition 2002,13:501-
510；Colloids and Surfaces B:Biointerfaces 2009,71:268-274) modification of chitosan so that shell gathers
The blood compatibility of sugar significantly improves.But these modes are not often high in the density of the Phosphorylcholine group of material surface, limit
It is made and the application in field and the further raising of blood compatibility is modified in bio-medical material.
Therefore, by the methacrylic acid containing Phosphorylcholine group-methylacryoyloxyethyl Phosphorylcholine binary copolymerization
Thing (PMA) polyanion, layer upon layer electrostatic self assembly is carried out with chitosan (polycation), is obtained with imitating cell outer-layer film knot
Coating surface (the Colloids and Surfaces B of structure:Biointerfaces 2011,85:48-55).Protein adsorbs
With platelet adhesion reaction test result indicates that：The blood compatibility on modified surface is obviously improved.In view of this modification side
The all the advantages of method, technical support will be provided to lift the blood compatibility of bio-medical material.However, with physical absorption side
Formula is incorporated in the polymer with simulated cellulosa membrane structure coating of transplanting device surface, occurs unavoidably in complex environment in vivo molten
Solve, come off.Therefore, Lewis and Xu build equality (Biomaterials 2001,22:99-111；Biomaterials 2004,
25:3099-3108；European Polymer Journal 2004,40:291-298) respectively to containing trimethoxy silicon substrate
The polymer coating of group and Phosphorylcholine group is studied.As a result show, trimethoxy on polymer molecular chain in coating
Silicon group meets water and can hydrolyze, be crosslinked, and also covalent bond can be formed with the active group of substrate surface, so that Phosphorylcholine class
The stability of polymer coating is significantly improved.As can be seen here, the crosslinking between polymer and its with substrate surface functional group
Reaction, be to improve Phosphorylcholine to birds of the same feather flock together the key factor of compound coating stability.
However, the polymer crosslinkable groups facile hydrolysis, crosslinking in building-up process so that its building-up process condition is excessively
Harshness, it is difficult to preserve, causes its application to be limited.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of epoxy radicals and mercapto
The method that base crosslinking prepares bionic coating.This method is simple and convenient to operate, and has imitating cell outer-layer membrane structure for acquisition stabilization
Coating surface provide a kind of new approach.This method is by by the phosphoryl choline polymer containing epoxy radicals and polymercaptan
Mixed solution is coated on chitosan film surface, and the phosphoryl choline polymer of good hydrophilic property passes through epoxy radicals and chitosan surface amino groups
Reaction be fixed on the surface of chitosan, obtain the surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves,
Advancing angle and receding angle substantially reduce.In addition, the presence of polymercaptan crosslinking agent adds chitosan surface Phosphorylcholine group
Content, so as to further increase the hydrophily of chitosan.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of epoxy radicals prepares imitative with sulfydryl crosslinking
The method of raw coating, it is characterised in that this method comprises the following steps：
Step 1: under nitrogen protection, by the vinyl monomer containing Phosphorylcholine group and the ethene containing epoxy radicals
Base monomer carries out Raolical polymerizable in the presence of initiator, obtains the phosphoryl choline polymer containing epoxy radicals；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in step 1 is dissolved in solvent, to obtain polymer molten
Liquid, polymercaptan then is added into the polymer solution, it is well mixed to obtain mixed solution；The mixed solution is coated on
Chitosan surface, immersion treatment 5h~24h 40 DEG C~90 DEG C under the conditions of is placed in distilled water after drying, in chitosan after taking-up
Surface obtains the bionic coating with imitating cell outer-layer membrane structure.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 1
Vinyl monomer is methacrylic monomer, acrylic monomer, methacryl amine monomer or acrylamide monomers.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 1
The mole of vinyl monomer containing Phosphorylcholine group is the vinyl monomer containing Phosphorylcholine group and contains epoxy
The 60%~90% of the integral molar quantity of the vinyl monomer of base.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 1
Vinyl monomer containing Phosphorylcholine group is methylacryoyloxyethyl Phosphorylcholine, the vinyl monomer containing epoxy radicals
For GMA.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 1
The reaction dissolvent of Raolical polymerizable is the mixed solvent of methanol and tetrahydrofuran, and reaction temperature is 70 DEG C~80 DEG C, reaction
Time is 12h~24h.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that the methanol and four
The volume ratio of hydrogen furans is (4~6):1.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that the methanol and four
The volume ratio of hydrogen furans is 5:1.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 1
Initiator is azodiisobutyronitrile, and the mole of initiator for the vinyl monomer containing Phosphorylcholine group and contains epoxy radicals
Vinyl monomer integral molar quantity 0.5%~1%.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 2
Solvent is the mixed solvent of methanol and acetone, and the volumn concentration of in the mixed solvent methanol is 50%~99%.
The method that a kind of above-mentioned epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that described in step 2
The concentration of the phosphoryl choline polymer containing epoxy radicals is 0.2mg/mL~5mg/mL in polymer solution, and the volume of polymercaptan is
The 0.25%~5% of polymer solution volume.
The present invention has advantages below compared with prior art：
1st, the present invention passes through the vinyl monomer containing Phosphorylcholine and the vinyl monomer containing epoxy radicals simple
Raolical polymerizable, the phosphoryl choline polymer containing epoxy radicals is synthesized, and itself and polymercaptan are dissolved in the mixed solvent, applied
Chitosan surface is overlayed on, immersion treatment in distilled water is placed in after drying, you can is prepared bionical with imitating cell outer-layer membrane structure
Coating, preparation method are simple and convenient to operate, and the coating surface with imitating cell outer-layer membrane structure to obtain stable provides one
The new approach of kind.
2nd, the present invention is by the way that the mixed solution of the phosphoryl choline polymer containing epoxy radicals and polymercaptan is gathered coated on shell
Sugared film surface, the phosphoryl choline polymer of good hydrophilic property are fixed on chitosan by the reaction of epoxy radicals and chitosan surface amino groups
Surface, obtain with imitating cell outer-layer membrane structure surface so that its hydrophily significantly improves, and advancing angle and receding angle are obvious
Reduce.In addition, the presence of polymercaptan crosslinking agent adds the content of chitosan surface Phosphorylcholine group, so as to further increase
The hydrophily of chitosan.
3rd, bionic coating of the invention will pass in blood purification, material implanted, organizational project, medicament slow release and biology
The fields such as sensor have broad application prospects.
With reference to the accompanying drawings and examples, technical scheme is described in further detail.
Brief description of the drawings
Fig. 1 is the dynamic of the bionic coating of chitosan film, bionic coating prepared by comparative example 1 and the preparation of the embodiment of the present invention 1
State contact angle.
Fig. 2 is the dynamic contact angle test chart for the bionic coating that the embodiment of the present invention 1 is prepared on chitosan film surface.
Embodiment
Embodiment 1
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol methyl-props
Olefin(e) acid ethylene oxidic ester carries out Raolical polymerizable, radical polymerization in the presence of initiator 0.1mmol azodiisobutyronitriles
It is 70 DEG C, time 24h to close reaction temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy at -50 DEG C
The phosphoryl choline polymer of base；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 5:1 volume
Than the mixed solvent of mixing；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 2mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 15 μ L polymercaptans are then added into the polymer solution, are mixed
Close solution；By the mixed solution drop coating in chitosan film surface, it is placed in after drying in distilled water, under the conditions of 90 DEG C at immersion
6h is managed, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
The volumn concentration of in the mixed solvent methanol is 99%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Using document (method and influence factor of accurate measure surface dynamic contact angle, Northwest University's journal (natural science
Version), Oct, 2011, Vol.41, No.5) disclosed in method determine the dynamic contact angle of bionic coating manufactured in the present embodiment,
As a result Fig. 2 is seen.The curve of mark 1,2 and 3 is respectively the advance of first circulation, second circulation and the 3rd circulation in figure
Angle, remaining curve are the receding angle of three circulations, and as seen from the figure, first circulation advancing angle is larger, and this is probably surface hydrophilic
Property Phosphorylcholine group move to coat inside, caused by surface hydrophobicity group is more.And two circulation advancing angles afterwards
Overlapped with receding angle, and as the increase advancing angle of pendulous frequency has the trend to diminish, the phosphinylidyne courage of this explanation good hydrophilic property
The content that alkali polymer is fixed on chitosan surface is higher so that with the increase of wetting time, its hydrophily significantly improves.
As can be seen here, bionic coating surface manufactured in the present embodiment, good bio-compatible will be kept under current intelligence in vivo
Property.
Comparative example 1
By the polymer solution drop coating of embodiment 1 in chitosan film surface, it is placed in after drying in distilled water, in 90 DEG C of conditions
Lower immersion treatment 6h, the bionic coating with imitating cell outer-layer membrane structure is obtained after taking-up on chitosan film surface.
As shown in figure 1, CS represents chitosan film in figure, CS-PMG represents the bionic coating of the preparation of comparative example 1, CS-PC-
PMG represents the bionic coating of the preparation of embodiment 1, and Ad represents advancing angle, and Re represents receding angle.It can be seen that embodiment 1
The advancing angle and receding angle of the bionic coating of preparation decrease, because the phosphoryl choline polymer of good hydrophilic property passes through
The reaction of epoxy radicals and chitosan surface amino groups is fixed on the surface of chitosan, obtains the table with imitating cell outer-layer membrane structure
Face so that its hydrophily significantly improves, and advancing angle and receding angle substantially reduce.In addition, the presence of polymercaptan crosslinking agent adds
The hydrophily of chitosan, advancing angle and receding angle all reduce.This explanation polymercaptan adds chitosan surface Phosphorylcholine group
Content.
Embodiment 2
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol acrylic acid
Ethylene oxidic ester carries out Raolical polymerizable in the presence of initiator 0.2mmol azodiisobutyronitriles, and radical polymerization is anti-
It is 80 DEG C, time 12h to answer temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy radicals at -50 DEG C
Phosphoryl choline polymer；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 6:1 volume ratio is mixed
The mixed solvent of conjunction；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 0.4mg step 1 is dissolved in methanol and acetone
In the mixed solvent obtains 2mL polymer solutions, and 5 μ L polymercaptans are then added into the polymer solution, well mixed to obtain
Mixed solution；By the mixed solution drop coating in chitosan film surface, it is placed in distilled water after drying, is soaked under the conditions of 40 DEG C
20h is handled, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
In the mixed solvent methanol volumn concentration be 90%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Embodiment 3
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 14mmol acrylyl oxy-ethyls Phosphorylcholine and 6mmol glycidyls
Ester carries out Raolical polymerizable in the presence of initiator 0.1mmol azodiisobutyronitriles, and Raolical polymerizable temperature is
75 DEG C, time 20h, reaction is dialysed after terminating, and is then freeze-dried at -50 DEG C, is obtained the Phosphorylcholine containing epoxy radicals
Polymer；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 4:The mixing of 1 volume ratio mixing
Solvent；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 10mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 100 μ L polymercaptans are then added into the polymer solution, it is well mixed to obtain
Mixed solution；By the mixed solution drop coating in chitosan film surface, it is placed in distilled water after drying, is soaked under the conditions of 80 DEG C
5h is handled, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
In the mixed solvent methanol volumn concentration be 60%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Embodiment 4
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 14mmol 2- Methacrylamides ethylphosphocholines and 6mmol acrylic acid
Ethylene oxidic ester carries out Raolical polymerizable in the presence of initiator 0.15mmol azodiisobutyronitriles, and radical polymerization is anti-
It is 70 DEG C, time 24h to answer temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy radicals at -50 DEG C
Phosphoryl choline polymer；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 5:1 volume ratio is mixed
The mixed solvent of conjunction；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 4mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 60 μ L polymercaptans are then added into the polymer solution, are mixed
Close solution；By the mixed solution drop coating in chitosan film surface, it is placed in after drying in distilled water, under the conditions of 70 DEG C at immersion
10h is managed, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
The volumn concentration of in the mixed solvent methanol is 50%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Embodiment 5
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 18mmol 2- Methacrylamides ethylphosphocholines and 2mmol methyl-props
Olefin(e) acid ethylene oxidic ester carries out Raolical polymerizable, radical polymerization in the presence of initiator 0.1mmol azodiisobutyronitriles
It is 70 DEG C, time 24h to close reaction temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy at -50 DEG C
The phosphoryl choline polymer of base；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 6:1 volume
Than the mixed solvent of mixing；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 6mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 80 μ L polymercaptans are then added into the polymer solution, are mixed
Close solution；By the mixed solution drop coating in chitosan film surface, it is placed in after drying in distilled water, under the conditions of 60 DEG C at immersion
10h is managed, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
The volumn concentration of in the mixed solvent methanol is 80%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Embodiment 6
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 12mmol 2- Methacrylamides ethylphosphocholines and 6mmol methyl-props
Olefin(e) acid ethylene oxidic ester carries out Raolical polymerizable, radical polymerization in the presence of initiator 0.1mmol azodiisobutyronitriles
It is 70 DEG C, time 24h to close reaction temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy at -50 DEG C
The phosphoryl choline polymer of base；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 4:1 volume
Than the mixed solvent of mixing；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 5mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 40 μ L polymercaptans are then added into the polymer solution, are mixed
Close solution；By the mixed solution drop coating in chitosan film surface, it is placed in after drying in distilled water, under the conditions of 50 DEG C at immersion
24h is managed, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
The volumn concentration of in the mixed solvent methanol is 99%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Embodiment 7
The present embodiment comprises the following steps：
Step 1: under nitrogen protection, by 12mmol 2- Methacrylamides ethylphosphocholines and 6mmol methyl-props
Olefin(e) acid ethylene oxidic ester carries out Raolical polymerizable, radical polymerization in the presence of initiator 0.2mmol azodiisobutyronitriles
It is 70 DEG C, time 24h to close reaction temperature, and reaction is dialysed after terminating, and is then freeze-dried, is obtained containing epoxy at -50 DEG C
The phosphoryl choline polymer of base；The reaction dissolvent of the Raolical polymerizable is methanol and tetrahydrofuran according to 5:1 volume
Than the mixed solvent of mixing；
Step 2: the phosphoryl choline polymer containing epoxy radicals described in 3mg step 1 is dissolved in the mixed of methanol and acetone
2mL polymer solutions are obtained in bonding solvent, 30 μ L polymercaptans are then added into the polymer solution, are mixed
Close solution；By the mixed solution drop coating in chitosan film surface, it is placed in after drying in distilled water, under the conditions of 75 DEG C at immersion
12h is managed, the bionic coating with imitating cell outer-layer membrane structure is obtained on chitosan film surface after taking-up；The methanol and acetone
The volumn concentration of in the mixed solvent methanol is 90%.
With 400MHz NMRs with D2O is the hydrogen of the phosphoryl choline polymer containing epoxy radicals prepared by solvent test
Nuclear-magnetism.Appearance is had no at 5~7ppm, shows do not have residual monomer in gained copolymer, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3Characteristic peak, polymer is calculated for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm
Composition, it is known that polymer composition is basically identical with rate of charge.
Bionic coating prepared by the embodiment of the present invention 1 to embodiment 7 compared with undressed chitosan film, advancing angle and
Receding angle decreases.Because the phosphoryl choline polymer containing epoxy passes through epoxy radicals and chitosan surface amino groups
Reaction is fixed on the surface of chitosan, obtains the surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves, preceding
Entering angle and receding angle substantially reduces.In addition, the presence of polymercaptan crosslinking agent adds containing for chitosan surface Phosphorylcholine group
Amount, adds the hydrophily of chitosan, advancing angle and receding angle all reduce.This explanation polymercaptan.
It is described above, only it is presently preferred embodiments of the present invention, any restrictions is not done to the present invention, it is every according to invention skill
Any simple modification, change and the equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (10)
1. a kind of method that epoxy radicals prepares bionic coating with sulfydryl crosslinking, it is characterised in that this method comprises the following steps：
Step 1: under nitrogen protection, by the vinyl monomer containing Phosphorylcholine group and the vinyl list containing epoxy radicals
Body carries out Raolical polymerizable in the presence of initiator, obtains the phosphoryl choline polymer containing epoxy radicals；
Polymer solution is obtained Step 2: the phosphoryl choline polymer containing epoxy radicals described in step 1 is dissolved in solvent,
Then polymercaptan is added into the polymer solution, it is well mixed to obtain mixed solution；The mixed solution is coated on shell
Glycan surface, immersion treatment 5h~24h 40 DEG C~90 DEG C under the conditions of is placed in distilled water after drying, in chitosan table after taking-up
Face obtains the bionic coating with imitating cell outer-layer membrane structure.
2. the method that a kind of epoxy radicals according to claim 1 prepares bionic coating with sulfydryl crosslinking, it is characterised in that step
Vinyl monomer described in rapid one is methacrylic monomer, acrylic monomer, methacryl amine monomer or propylene
Amide-type monomer.
3. the method that a kind of epoxy radicals according to claim 1 prepares bionic coating with sulfydryl crosslinking, it is characterised in that step
The mole of vinyl monomer containing Phosphorylcholine group described in rapid one is the vinyl monomer containing Phosphorylcholine group
With the 60%~90% of the integral molar quantity of the vinyl monomer containing epoxy radicals.
4. the method that a kind of epoxy radicals according to claim 1 prepares bionic coating with sulfydryl crosslinking, it is characterised in that step
Vinyl monomer containing Phosphorylcholine group described in rapid one is methylacryoyloxyethyl Phosphorylcholine, contains epoxy radicals
Vinyl monomer is GMA.
5. a kind of epoxy radicals according to any claim in Claims 1-4 prepares bionic coating with sulfydryl crosslinking
Method, it is characterised in that the reaction dissolvent of Raolical polymerizable described in step 1 is molten for the mixing of methanol and tetrahydrofuran
Agent, reaction temperature are 70 DEG C~80 DEG C, and the reaction time is 12h~24h.
6. the method that a kind of epoxy radicals according to claim 5 prepares bionic coating with sulfydryl crosslinking, it is characterised in that institute
The volume ratio for stating methanol and tetrahydrofuran is (4~6):1.
7. the method that a kind of epoxy radicals according to claim 6 prepares bionic coating with sulfydryl crosslinking, it is characterised in that institute
The volume ratio for stating methanol and tetrahydrofuran is 5:1.
8. a kind of epoxy radicals according to any claim in Claims 1-4 prepares bionic coating with sulfydryl crosslinking
Method, it is characterised in that initiator described in step 1 is azodiisobutyronitrile, and the mole of initiator is to contain Phosphorylcholine
The 0.5%~1% of the integral molar quantity of the vinyl monomer of group and vinyl monomer containing epoxy radicals.
9. a kind of epoxy radicals according to any claim in Claims 1-4 prepares bionic coating with sulfydryl crosslinking
Method, it is characterised in that solvent described in step 2 is the mixed solvent of methanol and acetone, the volume hundred of in the mixed solvent methanol
It is 50%~99% to divide content.
10. a kind of epoxy radicals according to any claim in Claims 1-4 prepares bionic coating with sulfydryl crosslinking
Method, it is characterised in that the concentration of the phosphoryl choline polymer containing epoxy radicals is in polymer solution described in step 2
0.2mg/mL~5mg/mL, the volume of polymercaptan are the 0.25%~5% of polymer solution volume.
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| 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 |
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| CN101531740A (en) * | 2009-01-12 | 2009-09-16 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN103881126A (en) * | 2014-04-06 | 2014-06-25 | 西安科技大学 | Method for improving blood compatibility of material |
| CN104744635A (en) * | 2015-04-17 | 2015-07-01 | 西安科技大学 | Preparation method of di-bionic polymer |
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| CN101531740A (en) * | 2009-01-12 | 2009-09-16 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN103881126A (en) * | 2014-04-06 | 2014-06-25 | 西安科技大学 | Method for improving blood compatibility of material |
| CN104744635A (en) * | 2015-04-17 | 2015-07-01 | 西安科技大学 | Preparation method of di-bionic polymer |
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| Fabrication and hemocompatibility of cell outer membrane mimetic surfaces on chitosan by layer by layer assembly with polyanion bearing phosphorylcholine groups;Ming Gong等;《Colloids and Surfaces B:Biointerfaces》;20101105;第85卷(第1期);48-55 * |
| 壳聚糖静电吸附羧基磷酰胆碱聚合物的研究;宫铭等;《功能材料》;20141215;第45卷(第23期);23038-23042 * |
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