CN106750450A - Preparation method containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating - Google Patents
Preparation method containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating Download PDFInfo
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- CN106750450A CN106750450A CN201610991756.6A CN201610991756A CN106750450A CN 106750450 A CN106750450 A CN 106750450A CN 201610991756 A CN201610991756 A CN 201610991756A CN 106750450 A CN106750450 A CN 106750450A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2443/02—Homopolymers or copolymers of monomers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses a kind of preparation method containing epoxy phosphoryl choline polymer Yu dopamine bionic coating,GMA monomer containing epoxy and the methylacryoyloxyethyl Phosphorylcholine monomer containing Phosphorylcholine hydrophilic radical are passed through into simple solution free radical polymerization,Phosphoryl choline polymer of the synthesis containing epoxy,And it is dissolved in polar solvent with dopamine,Being coated in needs modified material surface,It is placed in after drying in pH=8.5 Tris HCl/water solution and is heated,Make amino and chitosan film surface amino groups and dopamine crosslinking adhesion while epoxy reaction in phosphoryl choline polymer in dopamine,Phosphorylcholine group is fixed on chitosan film surface by the grappling and the adhesion of dopamine reacted by epoxy in phosphoryl choline polymer and chitosan film surface amino groups,The crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure can be prepared.
Description
Technical field
The present invention relates to material surface science and biological medical polymer material technical field, and in particular to one kind contains ring
Oxygen phosphoryl choline polymer adheres to the preparation method of bionic coating with dopamine crosslinking.
Background technology
Shitosan has the advantages that degradability, antibiotic property, nontoxic, non-stimulated, pH responses (Carbohydrate
Polymers2010,79:724-730), it has been widely used in the fields such as biomedicine.Increasing research shows:Shell
Glycan and its derivant material can be used for blood purification.Amino in chitosan molecule contributes to various toxin in blood
Absorption, can be used for blood Absorbent (SCI 2002,23:75-77;Journal of
Microencapsulation1993,10:475-486).Chitosan film has dialysance high, selectivity and intensity, Ke Yiyong
Make haemodialysis material (Journal of Applied Polymer Science 1992,46:255-261;263-269).Though
Right Chitosan-phospholipid complex has many advantages as blood purification material, but there is also protein absorption, blood platelet
Stick, ultimately result in blood coagulation, the problems such as form thrombus, so the blood compatibility for improving Chitosan-phospholipid complex material is compeled
The eyebrows and eyelashes (Applied Surface Science 2005,241:485-492;Biomaterials 2002,23:2561-2568;
Biomaterials2003,24:3213-3220).
Phosphorylcholine (phosphorylcholine, PC) is the terminal hydrophyllic group for constituting 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 interacts with physiological environment and will not only adsorb and depositing proteins, will not also trigger
Platelet activation, cause the adverse reactions such as blood coagulation, with good biocompatibility.Research in recent years shows, using phosphinylidyne
Choline group and its polymer build in material surface has imitating cell outer-layer membrane 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 is significantly improved.But, these modes are not often high in the density of the Phosphorylcholine group of material surface, limit
It has been made in the application in the modified field of bio-medical material and the further raising of blood compatibility.
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 shitosan (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 is adsorbed
With platelet adhesion reaction test result indicate that:The blood compatibility on modified surface is obviously improved.In view of this modified side
A variety of advantages of method, will provide technical support to lift the blood compatibility of bio-medical material.However, with physical absorption side
Formula combines the polymer with simulated cellulosa membrane structure coating in 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.Result shows, trimethoxy on polymer molecular chain in coating
Silicon group is met 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, between polymer crosslinking 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
It is harsh, be difficult to preserve, cause its range of application to be limited.
The content of the invention
To solve the above problems, adhesion is crosslinked with dopamine containing epoxy phosphoryl choline polymer the invention provides one kind
The preparation method of bionic coating.
To achieve the above object, the technical scheme taken of the present invention is:
Preparation method containing epoxy phosphoryl choline polymer Yu dopamine bionic coating, comprises the following steps:
S1, under nitrogen protection, the vinyl monomer containing epoxy and the vinyl monomer containing Phosphorylcholine are being drawn
Raolical polymerizable is carried out in the presence of hair agent, the phosphoryl choline polymer containing epoxy is obtained;
S2, the phosphoryl choline polymer containing epoxy of gained in dopamine and step S1 is dissolved in polar solvent and being mixed
Solution is closed, the mixed solution is then coated on material surface to be modified, dried;
S3, will be dried in step S2 after material to be modified be placed in the pH=8.5 Tris-HCl aqueous solution, 45 DEG C~
Heat 2h~12h under the conditions of 95 DEG C, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
Preferably, the vinyl monomer containing epoxy described in step S1 is GMA, described to contain
The vinyl monomer for having Phosphorylcholine is 2- methylacryoyloxyethyl Phosphorylcholines.
Preferably, the vinyl monomer containing Phosphorylcholine described in step S1 and the vinyl monomer mole containing epoxy
Than being about 9.5: 0.5~7: 3.
Preferably, the solvent of Raolical polymerizable described in step S1 be methyl alcohol and tetrahydrofuran according to 4: 1 volume
Than mixing gained, initiator is azodiisobutyronitrile, and reaction temperature is 70 DEG C, and the reaction time is 24h, is with molecular cut off
7000 bag filter is dialysed.
Preferably, the concentration of dopamine is 0.1mg/mL~0.5mg/mL in mixed solution described in step S2, containing aldehyde radical
Phosphoryl choline polymer concentration be 0.2mg/mL~5mg/mL.
Preferably, polar solvent described in step S2 is methyl alcohol or ethanol.
Preferably, material to be modified described in step S2 is shitosan.
The invention has the advantages that:
1st, the present invention is by the GMA monomer containing epoxy and contains Phosphorylcholine hydrophilic radical
Methylacryoyloxyethyl Phosphorylcholine monomer by simple solution free radical polymerization, synthesize the Phosphorylcholine containing epoxy
Polymer, and it is dissolved in polar solvent with dopamine, being coated in needs modified material surface, and pH=is placed in after drying
The treatment of 8.5 Tris-HCl heated in water solution, makes amino and chitosan film surface amino groups and phosphoryl choline polymer in dopamine
Dopamine crosslinking adhesion while middle epoxy reaction, reacts by epoxy in phosphoryl choline polymer and chitosan film surface amino groups
Grappling and the adhesion of dopamine Phosphorylcholine group is fixed on chitosan film surface, you can preparing has imitating cell outer-layer
The crosslinking adhesion bionic coating of membrane structure.
2nd, the preparation method of imitating cell outer-layer membrane structure coating of the invention is simple and convenient to operate, to obtain the tool of stabilization
The coating surface for having imitating cell outer-layer membrane structure provides a kind of new approach.
3rd, imitating cell outer-layer membrane structure coating of the invention will, organizational project material implanted in blood purification, medicine
The field such as sustained release and biology sensor has broad application prospects.
Brief description of the drawings
Fig. 1 is the dynamic contact angle of chitosan film of the present invention and Chitosan film.
Fig. 2 is chitosan film of the present invention and Chitosan film surface fine energy spectrum diagram.
Specific embodiment
In order that objects and advantages of the present invention become more apparent, the present invention is carried out further with reference to embodiments
Describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
Embodiment 1
16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
With 400MHz NMRs with D2O is the proton magnetic of solvent test polymer.Appearance is had no at 5~7ppm,
Show there is no residual monomer in gained copolymer, and successfully synthesize the polymer, with 3.28ppm at as-N+(CH3)3Feature
Peak, for the peak of methylene and pendant methyl on main chain calculates polymer composition at 0.9~2.2ppm, it is known that the polymer constitute with
Rate of charge is basically identical.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 1mg/mL, so
After add dopamine 0.5g be well mixed.It is again that the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine is molten
Drop-coated is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry rearmounted
5h is processed at 80 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Phosphorylcholine group is fixed on chitosan film surface by the grappling of base reaction and the adhesion of dopamine, you can is prepared to have and is imitated thin
The crosslinking adhesion bionic coating of extracellular film structure.
As shown in figure 1, the present embodiment through the chitosan film of coating treatment compared with the chitosan film without coating treatment, warp
The advancing angle and receding angle of the shitosan of coating treatment decrease, because the phosphoryl choline polymer of good hydrophilic property leads to
The reaction of epoxy and amino in the reaction of shitosan surface amino groups and dopamine is crossed, Phosphorylcholine group is adhered fixed in shell
The surface of glycan film, surface of the acquisition with imitating cell outer-layer membrane structure so that its hydrophily is significantly improved, advancing angle and retrogressing
Angle substantially reduces.Additionally, the presence of dopamine increased the hydrophily of modification of chitosan, advancing angle and receding angle are all reduced.This
Illustrate that dopamine increased the content of chitosan film surface Phosphorylcholine group.
As shown in Fig. 2 the present embodiment through the chitosan film of coating treatment compared with the chitosan film without coating treatment, warp
There are N and P characteristic absorption peaks on Phosphorylcholine group on the chitosan film surface of modification, the Phosphorylcholine of this explanation good hydrophilic property
Group is fixed on chitosan film surface.Amino and chitosan film surface amino groups and epoxy in phosphoryl choline polymer in dopamine
Dopamine crosslinking while reaction, the grappling reacted by epoxy in phosphoryl choline polymer and chitosan film surface amino groups and
Phosphorylcholine group is fixed on chitosan film surface by the adhesion of dopamine, can prepare the table with imitating cell outer-layer membrane structure
, there are N and P characteristic absorption peaks on Phosphorylcholine group in face so that its hydrophily is significantly improved.
Embodiment 2
14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 2mg/mL, so
After add dopamine 1g be well mixed.Again by the mixed solution of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine
Drop coating is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy are placed in after drying
12h is processed at 45 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Base reacts grappling and Phosphorylcholine group is fixed on chitosan film surface by the adhesion of dopamine, you can preparing has imitative cell
The crosslinking adhesion bionic coating of outer layer membrane structure.
Embodiment 3
19mmol 2- methylacryoyloxyethyls Phosphorylcholines and 1mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 5mg/mL, so
After add dopamine 0.8g be well mixed.It is again that the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine is molten
Drop-coated is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry rearmounted
2h is processed at 95 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Base reacts grappling and Phosphorylcholine group is fixed on chitosan film surface by the adhesion of dopamine, you can preparing has imitative cell
The crosslinking adhesion bionic coating of outer layer membrane structure.
Embodiment 4
15mmol 2- methylacryoyloxyethyls Phosphorylcholines and 5mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 4mg/mL, so
After add dopamine 0.6g be well mixed.It is again that the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine is molten
Drop-coated is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry rearmounted
4h is processed at 60 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Base reacts grappling and Phosphorylcholine group is fixed on chitosan film surface by the adhesion of dopamine, you can preparing has imitative cell
The crosslinking adhesion bionic coating of outer layer membrane structure.
Embodiment 5
17mmol 2- methylacryoyloxyethyls Phosphorylcholines and 3mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 3mg/mL, so
After add dopamine 0.4g be well mixed.It is again that the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine is molten
Drop-coated is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry rearmounted
6h is processed at 70 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Base reacts grappling and Phosphorylcholine group is fixed on chitosan film surface by the adhesion of dopamine, you can preparing has imitative cell
The crosslinking adhesion bionic coating of outer layer membrane structure.
Embodiment 6
18mmol 2- methylacryoyloxyethyls Phosphorylcholines and 2mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 1mg/mL, so
After add dopamine 0.2g be well mixed.It is again that the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine is molten
Drop-coated is on shitosan surface.The phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry rearmounted
8h is processed at 80 DEG C in the pH=8.5 Tris-HCl aqueous solution, makes amino and chitosan film surface amino groups and phosphinylidyne in dopamine
Dopamine crosslinking while epoxy reaction in choline polymer, by epoxy in phosphoryl choline polymer and chitosan film surface ammonia
Phosphorylcholine group is fixed on chitosan film surface by base grappling and the adhesion of dopamine, you can preparing has imitating cell outer-layer
The crosslinking adhesion bionic coating of membrane structure.
Embodiment 7
14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol GMAs are weighed, with
0.1mmol azodiisobutyronitriles are initiator, and methyl alcohol and tetrahydrofuran are solvent, under nitrogen protection, 70 DEG C of polymerisations
24h, reaction is dialysed after terminating, and the then freeze-drying at -50 DEG C obtains the phosphoryl choline polymer containing epoxy.
Phosphoryl choline polymer containing epoxy manufactured in the present embodiment is configured to the methanol solution of 2mL, 0.2mg/mL,
Then dopamine 0.3g is added to be well mixed.Again by the mixing of the above-mentioned phosphoryl choline polymer containing epoxy and dopamine
Solution drop coating is on shitosan surface.After the phosphoryl choline polymer and the mixed solution of dopamine that wherein drop coating contains epoxy dry
Be placed in the pH=8.5 Tris-HCl aqueous solution and process 10h at 50 DEG C, make in dopamine amino and chitosan film surface amino groups with
Dopamine crosslinking while epoxy reaction in phosphoryl choline polymer, by epoxy in phosphoryl choline polymer and chitosan film table
Phosphorylcholine group is fixed on chitosan film surface by face amino reaction grappling and the adhesion of dopamine, you can is prepared to have and is imitated
The crosslinking adhesion bionic coating of cell outer-layer membrane structure.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. the preparation method containing epoxy phosphoryl choline polymer Yu dopamine bionic coating, it is characterised in that including following step
Suddenly:
S1, under nitrogen protection, by the vinyl monomer containing epoxy and the vinyl monomer containing Phosphorylcholine in initiator
In the presence of carry out Raolical polymerizable, obtain the phosphoryl choline polymer containing epoxy;
S2, by dopamine and step S1 gained the phosphoryl choline polymer containing epoxy be dissolved in polar solvent obtain mixing it is molten
Liquid, is then coated on material surface to be modified by the mixed solution, dries;
S3, will be dried in step S2 after material to be modified be placed in the pH=8.5Tris-HCl aqueous solution, in 45 DEG C~95 DEG C bars
Heat 2h~12h under part, obtain the crosslinking adhesion bionic coating with imitating cell outer-layer membrane structure.
2. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that the vinyl monomer containing epoxy described in step S1 is GMA, described to contain
The vinyl monomer for having Phosphorylcholine is 2- methylacryoyloxyethyl Phosphorylcholines.
3. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that the vinyl monomer containing Phosphorylcholine described in step S1 rubs with the vinyl monomer containing epoxy
That ratio about 9.5: 0.5~7: 3.
4. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that the solvent of Raolical polymerizable described in step S1 be methyl alcohol and tetrahydrofuran according to 4: 1 volume
Than mixing gained, initiator is azodiisobutyronitrile, and reaction temperature is 70 DEG C, and the reaction time is 24h, is with molecular cut off
7000 bag filter is dialysed.
5. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that the concentration of dopamine is 0.1mg/mL~0.5mg/mL in mixed solution described in step S2, containing aldehyde radical
Phosphoryl choline polymer concentration be 0.2mg/mL~5mg/mL.
6. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that polar solvent described in step S2 is methyl alcohol or ethanol.
7. the preparation containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating according to claim 1
Method, it is characterised in that material to be modified described in step S2 is shitosan.
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CN108715643A (en) * | 2018-06-14 | 2018-10-30 | 西安科技大学 | A kind of preparation method of epoxy and amino phosphoryl choline polymer bionic adhesion coating |
CN108715644A (en) * | 2018-06-14 | 2018-10-30 | 西安科技大学 | A kind of preparation method of aldehyde radical and amino phosphoryl choline polymer bionic adhesion coating |
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