CN108659168A - A kind of double Biomimetic Polymers and the preparation method and application thereof - Google Patents
A kind of double Biomimetic Polymers and the preparation method and application thereof Download PDFInfo
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- CN108659168A CN108659168A CN201810539671.3A CN201810539671A CN108659168A CN 108659168 A CN108659168 A CN 108659168A CN 201810539671 A CN201810539671 A CN 201810539671A CN 108659168 A CN108659168 A CN 108659168A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to a kind of double Biomimetic Polymers based on the synthesis of pentafluorophenyl group graft reaction, and preparation method and application are further disclosed.Double Biomimetic Polymers of the present invention carry out Raolical polymerizable using the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing pentafluorophenyl group as raw material, obtain the phosphoryl choline polymer containing pentafluorophenyl group, and imitative bivalves attachment proteins ingredient dopamine is combined with the phosphoryl choline polymer containing pentafluorophenyl group, adjacent two phenolic hydroxyl groups have the adhesive attraction of imitative bivalves attachment proteins dopamine, assign water-soluble polymer the adhesion property excellent in material surface, Phosphorylcholine has the antifouling property of imitating cell outer-layer membrane structure, obtain the performance of good stable against biological contamination, the polymer has dual bionical feature, it has broad application prospects in material surface modification field.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to one kind being based on five
Double Biomimetic Polymers of fluorophenyl graft reaction synthesis, and preparation method and application are further disclosed.
Background technology
Biocompatibility refers to that various biologies, physics, chemistry generated after interacting between material and organism etc. is anti-
The conception of species answered.Generally speaking, be exactly material implantation human body after with human body compatibility, that is to say, that whether can be to human body group
Weave into toxic action.Under normal conditions, non-specific adsorption albumen is also easy to produce when general material is used in organism, activation is mended
Body molecule and immune system, so as to cause blood coagulation, immune and inflammatory reaction, so that its performance significantly reduces, even fails, this is just
It is due to the poor reason of Biocompatibility.Thus, Study on biocompatibility has become in biomaterial research field
Matter of utmost importance.
Since material surface is the medium that material is contacted with organism, the charge of material surface, parent/hydrophobicity, chemical group
All it is an important factor for influencing interfacial interaction between material and organism at, pattern etc., and determines material bio-compatible
Property whether excellent principal element.Therefore, the biocompatibility for improving material surface is the key that solve this problem in science.And
Substance with good biocompatibility is introduced into material surface to be modified, is the phase improved between material and organism
Interaction improves the most simple and effective approach of Biocompatibility.Therefore, the biocompatibility modification of material surface is raw
An eternal theme in object investigation of materials field has important academic significance and huge application prospect.
It has been reported and shows endothelial cell, albumin, heparin and/or polyethylene glycol with good blood compatibility
It is introduced into material surface, its biocompatibility can be obviously improved, especially significantly improves its blood compatibility.But it is above-mentioned
It there is various, such as endothelial cell and material in modified material for improving material surface biocompatibility
Expect the problems such as interaction on surface is poor, anti-blood impact capacity is bad, easy to fall off；And due to albumin and activity in vivo
Component causes the albumin content for being adsorbed on material surface to reduce, or even denaturation in material surface competitive Adsorption；And the heparin Yishui River
Solution, causes its activity to be decreased obviously, so that the complication such as induction bleeding, thrombopenia；In fierce respiratory, poly- second
Glycol is aoxidized because of superoxide anion and hydrogen peroxide, and also there is different degrees of biological pollution on surface.As it can be seen that being currently used for changing
The performance of the modified material of kind material surface biocompatibility is unsatisfactory.
Phosphorylcholine (phosphorylcholine, PC) is the terminal hydrophyllic group for forming cell membrane basic unit lecithin, is
Outer layer functional group in extracellular tunic, simultaneous with positive and negative xenogenesis 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 cause
Platelet activation leads to the adverse reactions such as blood coagulation, has good biocompatibility.In recent years studies have shown that 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.
It is existing carry out material surface biocompatibility modification method be mainly physics coating, that is, include dip-coating, spin coating and
The modes such as drop coating, and be structure imitating cell outer-layer membrane structure because it has the advantages that simple for process, easy to operate and mild condition
Obtain the promising approach on superior bio compatibility surface.However, for Phosphorylcholine modified material, due to the parent of its group
It is aqueous relatively strong so that the phosphoryl choline polymer coating that material surface is coated in by physics is easy in complicated physiological environment
Dissolving occurs, degradation, even falls off.It is then desired to which cross-linking or covalent bond group is introduced into phosphoryl choline polymer, pass through
Chemical reaction is crossed to be crosslinked the polymer coating or covalent bonding is in material surface.This undoubtedly increases this kind of Phosphorylcholine polymerization
Object synthesizes and application is to the difficulty of surface requirements, but also the tediously long complexity of the processing procedure of the technology, therefore, there is an urgent need to study
Exploitation uses simple, widely applicable surface modifying method.
Invention content
For this purpose, technical problem to be solved by the present invention lies in a kind of double Biomimetic Polymers are provided, to solve the prior art
Middle phosphoryl choline polymer carries out coating when material surface biocompatibility is modified and is easy to happen dissolving, degradation, even falls off
Problem；
Second technical problem that the present invention solves is to provide the preparation method of above-mentioned double Biomimetic Polymers.
In order to solve the above technical problems, a kind of preparation method of double Biomimetic Polymers of the present invention, including walk as follows
Suddenly：
(1) under inert gas protection, with the vinyl monomer containing Phosphorylcholine group and contain the second of pentafluorophenyl group
Alkenyl monomer is raw material, and Raolical polymerizable is carried out under the action of initiator, obtains the Phosphorylcholine containing pentafluorophenyl group
Polymer；
(2) phosphoryl choline polymer containing pentafluorophenyl group is dissolved in polar solvent, obtains polymer solution；And
Dopamine is added, under inert gas protection, graft reaction is carried out in 30-55 DEG C；Gained reactant is freeze-dried to get institute
Need double Biomimetic Polymers.
In the step (1), the vinyl monomer containing Phosphorylcholine group and the second containing pentafluorophenyl group
The molar ratio of alkenyl monomer is 3：7-8：2.
In the step (1)：
The vinyl monomer containing Phosphorylcholine group includes methylacryoyloxyethyl Phosphorylcholine；
The vinyl monomer containing pentafluorophenyl group includes methacrylic acid pentafluorophenyl esters.
In the step (1), the temperature for controlling the Raolical polymerizable is 60-80 DEG C.
Further include the steps that reaction raw materials are added in organic solvent to carry out Raolical polymerizable in the step (1),
The organic solvent is tetrahydrofuran, and the mixed solution added with ethyl alcohol or methanol.The dosage of the organic solvent is to realize
The abundant dissolving of the reaction raw materials is advisable.
In the step (2), the mole of the dopamine is in the phosphoryl choline polymer containing pentafluorophenyl group
The 10-120% of pentafluorophenyl group mole.
In the step (2), the polar solvent includes water, methanol or ethyl alcohol.The dosage of the polar solvent and make
The abundant solvent of reaction raw materials is advisable.
In the step (2), the temperature for controlling the graft reaction is 30-55 DEG C.
Further include the steps that gained reactant is dialysed in the step (1) and/or step (2).
The invention also discloses the double Biomimetic Polymers being prepared by the method.
The invention also discloses double Biomimetic Polymers for carrying out material surface biocompatibility modification
Purposes.
Double Biomimetic Polymers of the present invention are with the vinyl monomer containing Phosphorylcholine group and contain pentafluorophenyl group
Vinyl monomer is that raw material carries out Raolical polymerizable, obtains the phosphoryl choline polymer containing pentafluorophenyl group, and by imitative freshwater mussel
Class attachment proteins ingredient dopamine is combined with the phosphoryl choline polymer containing pentafluorophenyl group, and adjacent two phenolic hydroxyl groups have imitative bivalves
The adhesive attraction of attachment proteins dopamine assigns water-soluble polymer the adhesion property excellent in material surface, Phosphorylcholine tool
The antifouling property for having imitating cell outer-layer membrane structure obtains the performance of good stable against biological contamination, which has dual imitative
Raw feature has broad application prospects in material surface modification field.
DOPA amine groups in double Biomimetic Polymers of the present invention remove have a variety of non-covalent bond effects such as pi-pi accumulation it
Outside, also oxidizable polymerization forms adhesiveness poly-dopamine (PDA), can be with a variety of base materials including metal, glass and plastics
Generate water-fast strong adhesive attraction.In addition, dopamine coating can have biology by Michael's addition or schiff base reaction grafting
The molecule of function.The surface modification method of this imitative bivalves adherency can make up current physics coating and have to pass through complicated chemistry
Processing could obtain the limitation of stable coatings, simplify the condition and process of material surface modifying.Moreover, preparation of the present invention
Method, which is reacted using pentafluorophenyl group with amino, is grafted to dopamine on the phosphoryl choline polymer containing pentafluorophenyl group, Ke Yilve
The protection process for removing phenolic hydroxyl group solves since the phenolic hydroxyl group in DOPA amine monomers is the polymerization inhibitor of free radical polymerization, leads to this
The process that phenolic hydroxyl group protection must be carried out when class monomer polymerization, solves the difficulties of existing Dopaminergics Macroscopic single crystal；
Moreover, in double Biomimetic Polymers prepared by the method for the present invention, not only the grafting rate of the dopamine is controllable, and grafting rate is up to
65%, middle conventional method is only the grafting rate of 4% dopamine compared with the existing technology, and double Biomimetic Polymers are made in the present invention
Coating adhesion further enhances, and not easily to fall off.
Double bionical derivative of the present invention, with containing cellulosa film component Phosphorylcholine and bivalves attachment proteins ingredient
Double Biomimetic Polymers of dopamine are modified material surface, and the dopamine side group in polymer is can be adhered from aqueous solution to packet
The surfaces of various materials including polytetrafluoroethylene (PTFE) is included, Phosphorylcholine side group then automatically forms imitating cell outer-layer film knot in coating surface
Structure significantly improves the biocompatibility of base material.The double Biomimetic Polymers prepared using the method for the present invention are implanted into vivo
The fields such as material, organizational project, medicament slow release and biosensor have broad application prospects.
The preparation method of double bionical derivatives of the present invention, material source is extensive, and preparation method is simple, mild condition,
And grafting rate is controllable, and solve the problems, such as that purification of products is difficult in the prior art, provide one to obtain double Biomimetic Polymers
The new approach of kind.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the dynamic contact angle of chitosan film of the present invention and Chitosan film, and left side column is advancing angle in each group
Numerical value, right side column are receding angle numerical value；
Fig. 2 is chitosan film of the present invention and Chitosan film surface fine energy spectrum diagram.
Specific implementation mode
Graft reaction of the preparation based on pentafluorophenyl group of double Biomimetic Polymers described in the following embodiments of the present invention carries out, tool
Body synthetic route is as follows：
Embodiment 1
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 8mmol2- methacryloxyethyls Phosphorylcholine and 2mmol methacrylic acid phenyl-pentafluorides accurately are weighed
Ester, with ethyl alcohol and tetrahydrofuran mixed solvent (volume ratio 4：1) dissolving is uniformly mixed, by 0.1mmol azodiisobutyronitriles with four
Hydrogen furans dissolves to obtain initiator solution, in N2It protects, under 70 DEG C of stirring conditions, the mixing that monomer is added into three-necked bottle is molten
Liquid after preheating 30min, is added the initiator solution the reaction was continued for 24 hours, after reaction, concentration of reaction solution, with retention molecule
Amount is that the bag filter of 6000-8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain
Phosphoryl choline polymer containing pentafluorophenyl group；Nuclear-magnetism test result shows the molar content of pentafluorophenyl group in the polymer about
It is 17%；
With 400MHz Nuclear Magnetic Resonance with D2O is the proton magnetic of solvent test polymer.Appearance, table are had no at 5-7ppm
There is no residual monomer in bright gained copolymer, and successfully synthesize the polymer, at 3.28ppm be-N+(CH3)3Characteristic peak,
Polymer composition is calculated for methylene on main chain and the peak of pendant methyl, it is known that the polymer forms and feeds intake at 0.9-2.2ppm
Than almost the same；
(2) phosphoryl choline polymer containing pentafluorophenyl group obtained in 0.5g above-mentioned steps (1) is taken to be dissolved in 20mL
Polymer solution is obtained in methanol, and in N2Protection, under 30 DEG C of stirring conditions, it is molten that the polymer is added into three-necked bottle
Liquid preheats 30min, adds 0.15g dopamines, carries out insulated and stirred and reacts 12h；After reaction, concentration of reaction solution, with cut
Stay the bag filter that molecular weight is 6000-8000D dialyse in the aqueous hydrochloric acid solution that pH value is 3-4 concentration after reaction solution, will be saturating
Sample after analysis is freeze-dried at -50 DEG C, you can obtains double Biomimetic Polymers.After testing and calculate, it is poly- obtained by the present embodiment
The grafting rate for closing dopamine in object is 11%.
Embodiment 2
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 7mmol2- methacryloxyethyls Phosphorylcholine and 3mmol methacrylic acid pentafluorophenyl esters are weighed, is used
Methanol and the dissolving of tetrahydrofuran mixed solvent are uniformly mixed (volume ratio 4：1), by 0.1mmol azodiisobutyronitrile tetrahydrofurans
Dissolving obtains initiator solution, in N2It protects, under 60 DEG C of stirring conditions, the mixed solution of monomer, preheating is added into three-necked bottle
After 30min, the reaction was continued for addition initiator solution for 24 hours, and after reaction, concentration of reaction solution is 6000- with molecular cut off
The bag filter of 8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain containing pentafluorophenyl group
Phosphoryl choline polymer；Nuclear-magnetism test result shows that the molar content of pentafluorophenyl group in the polymer is about 26%；
(2) phosphoryl choline polymer containing pentafluorophenyl group obtained in 0.5g above-mentioned steps (1) is taken to be dissolved in 20mL
Polymer solution is obtained in ethyl alcohol, in N2Protection, under 35 DEG C of stirring conditions, the polymer solution is added into three-necked bottle,
30min is preheated, 0.2g dopamines are added, insulated and stirred reacts 14h；After reaction, concentration of reaction solution uses molecular cut off
For 6000-8000D bag filter dialyse in the aqueous hydrochloric acid solution that pH value is 3-4 concentration after reaction solution, by the sample after dialysis
Product are freeze-dried at -50 DEG C, you can obtain double Biomimetic Polymers.After testing and calculate, it is more in the present embodiment resulting polymers
The grafting rate of bar amine is 19%.
Embodiment 3
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 6mmol 2- methacryloxyethyls Phosphorylcholines and 4mmol methacrylic acid phenyl-pentafluorides accurately are weighed
Ester is uniformly mixed (volume ratio 4 with ethyl alcohol and the dissolving of tetrahydrofuran mixed solvent：1), by 0.1mmol azodiisobutyronitriles with four
Hydrogen furans dissolves to obtain initiator solution, in N2It protects, under 80 DEG C of stirring conditions, the mixing that monomer is added into three-necked bottle is molten
Liquid, after preheating 30min, the reaction was continued for addition initiator solution for 24 hours, and after reaction, concentration of reaction solution is with molecular cut off
The bag filter of 6000-8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain containing five fluorine
The phosphoryl choline polymer of phenyl；Nuclear-magnetism test result shows that the molar content of pentafluorophenyl group in the polymer is about 38%；
(2) phosphoryl choline polymer containing pentafluorophenyl group obtained in 0.5g above-mentioned steps (1) is taken to be dissolved in 20mL
Polymer solution is obtained in distilled water, in N2It protects, under 40 DEG C of stirring conditions, the polymer solution is added into three-necked bottle,
30min is preheated, 0.4g dopamines are added, insulated and stirred reacts 16h；After reaction, concentration of reaction solution uses molecular cut off
For 6000-8000D bag filter dialyse in the aqueous hydrochloric acid solution that pH value is 3-4 concentration after reaction solution, by the sample after dialysis
Product are freeze-dried at -50 DEG C, you can obtain double Biomimetic Polymers.After testing and calculate, it is more in the present embodiment resulting polymers
The grafting rate of bar amine is 31%.
Embodiment 4
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 5mmol 2- methacryloxyethyls Phosphorylcholines and 5mmol methacrylic acid pentafluorophenyl esters are weighed, is used
Methanol and the dissolving of tetrahydrofuran mixed solvent are uniformly mixed (volume ratio 4：1), by 0.1mmol azodiisobutyronitrile tetrahydrofurans
Dissolving obtains initiator solution, in N2It protects, under 65 DEG C of stirring conditions, the mixed solution of monomer, preheating is added into three-necked bottle
After 30min, the reaction was continued for addition initiator solution for 24 hours, and after reaction, concentration of reaction solution is 6000- with molecular cut off
The bag filter of 8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain containing pentafluorophenyl group
Phosphoryl choline polymer；Nuclear-magnetism test result shows that the molar content of pentafluorophenyl group in the polymer is about 47%；
(2) phosphoryl choline polymer containing pentafluorophenyl group obtained in 0.5g steps (1) is taken to be dissolved in 20mL methanol
In obtain polymer solution, in N2It protects, under 45 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, preheat
30min, adds 0.2g dopamines, and insulated and stirred reacts 18h.After reaction, concentration of reaction solution is with molecular cut off
Reaction solution of the bag filter of 6000-8000D in the aqueous hydrochloric acid solution that pH value is 3-4 after dialysis concentration, by the sample after dialysis
It is freeze-dried at -50 DEG C, you can obtain double Biomimetic Polymers.It after testing and calculates, DOPA in the present embodiment resulting polymers
The grafting rate of amine is 40%.
Embodiment 5
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 4mmol 2- methacryloxyethyls Phosphorylcholines and 6mmol methacrylic acid pentafluorophenyl esters are weighed, is used
Methanol and the dissolving of tetrahydrofuran mixed solvent are uniformly mixed (volume ratio 4：1), by 0.1mmol azodiisobutyronitrile tetrahydrofurans
Dissolving obtains initiator solution, in N2It protects, under 75 DEG C of stirring conditions, the mixed solution of monomer, preheating is added into three-necked bottle
After 30min, the reaction was continued for addition initiator solution for 24 hours, and after reaction, concentration of reaction solution is 6000- with molecular cut off
The bag filter of 8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain containing pentafluorophenyl group
Phosphoryl choline polymer；Nuclear-magnetism test result shows that the molar content of pentafluorophenyl group in the polymer is about 57%；
(2) it takes the phosphoryl choline polymer containing pentafluorophenyl group described in 0.5g steps (1) to be dissolved in 20mL ethyl alcohol to obtain
Polymer solution, in N2It protects, under 50 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, preheat 30min, then
0.5g dopamines are added, insulated and stirred reacts 20h.After reaction, concentration of reaction solution is 6000-8000D with molecular cut off
Bag filter pH value be 3-4 aqueous hydrochloric acid solution in dialysis concentration after reaction solution, the sample after dialysis is cold at -50 DEG C
It is lyophilized dry, you can obtain double Biomimetic Polymers.It after testing and calculates, the grafting rate of dopamine is in the present embodiment resulting polymers
49%.
Embodiment 6
The preparation method of double Biomimetic Polymers described in the present embodiment includes the following steps：
(1) 3mmol 2- methacryloxyethyls Phosphorylcholines and 7mmol methacrylic acid pentafluorophenyl esters are weighed, is used
Methanol and the dissolving of tetrahydrofuran mixed solvent are uniformly mixed (volume ratio 4：1), by 0.1mmol azodiisobutyronitrile tetrahydrofurans
Dissolving obtains initiator solution, in N2It protects, under 70 DEG C of stirring conditions, the mixed solution of monomer, preheating is added into three-necked bottle
After 30min, the reaction was continued for addition initiator solution for 24 hours, and after reaction, concentration of reaction solution is 6000- with molecular cut off
The bag filter of 8000D is dialysed；Finally, the sample after dialysis is freeze-dried at -50 DEG C, you can obtain containing pentafluorophenyl group
Phosphoryl choline polymer；Nuclear-magnetism test result shows that the molar content of pentafluorophenyl group in the polymer is about 71%；
(2) it takes the phosphoryl choline polymer containing pentafluorophenyl group described in 0.5g steps (1) to be dissolved in 20mL distilled water to obtain
To polymer solution, in N2It protects, under 55 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, preheats 30min,
0.7g dopamines are added, insulated and stirred is reacted for 24 hours.After reaction, concentration of reaction solution is 6000- with molecular cut off
Reaction solution of the bag filter of 8000D in the aqueous hydrochloric acid solution that pH value is 3-4 after dialysis concentration, by the sample after dialysis -50
It is freeze-dried at DEG C, you can obtain double Biomimetic Polymers.It after testing and calculates, dopamine connects in the present embodiment resulting polymers
Branch rate is 65%.
Double Biomimetic Polymers of the present invention can be used for the biocompatibility on modified material surface, have particular application as passing through by
Double Biomimetic Polymers obtained are dissolved in polar solvent, and are dripped Tu in material film surface to be modified, are waited drying and are placed on pH
In 30-80 DEG C of processing in=8.0-9.0 aqueous solutions, by pentafluorophenyl group in phosphoryl choline polymer and chitosan film surface amino groups
Phosphorylcholine group is fixed on chitosan film surface by the anchoring effect of nucleophilic substitution and the adherency of dopamine, you can system
The standby adherency bionic coating with imitating cell outer-layer membrane structure.
As shown in Figure 1, chitosan film of the present embodiment through coating treatment compared with the chitosan film without coating treatment, passes through
The advancing angle and receding angle of the chitosan of coating treatment decrease, this is because the phosphoryl choline polymer of good hydrophilic property is logical
Pentafluorophenyl group is crossed to be adhered fixed Phosphorylcholine group with the adherency for reacting anchoring and dopamine of chitosan surface amino groups
The surface of chitosan film obtains the surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves, and advancing angle is with after
Angle is moved back to be substantially reduced.
As shown in Fig. 2, chitosan film of the present embodiment through coating treatment compared with the chitosan film without coating treatment, passes through
There are N and P characteristic absorption peaks on Phosphorylcholine group on the chitosan film surface of modification, this illustrates the Phosphorylcholine of good hydrophilic property
Group is fixed on chitosan film surface.The viscous of anchoring and dopamine is reacted by pentafluorophenyl group and chitosan surface amino groups
It is attached that Phosphorylcholine group is adhered fixed on the surface of chitosan film so that its hydrophily significantly improves, and Phosphorylcholine base occurs
N and P characteristic absorption peaks in group.As it can be seen that the method for the invention can have the biocompatibility on chitosan material surface
The improvement of effect.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of double Biomimetic Polymers, which is characterized in that include the following steps：
(1) under inert gas protection, with the vinyl monomer containing Phosphorylcholine group and contain the vinyl of pentafluorophenyl group
Monomer is raw material, and Raolical polymerizable is carried out under the action of initiator, obtains the Phosphorylcholine polymerization containing pentafluorophenyl group
Object；
(2) phosphoryl choline polymer containing pentafluorophenyl group is dissolved in polar solvent, obtains polymer solution；And lazy
Property gas shield under, be added dopamine carry out graft reaction；Gained reactant is freeze-dried to get required double bionical polymerizations
Object.
2. the preparation method of double Biomimetic Polymers according to claim 1, which is characterized in that described in the step (1)
The molar ratio of vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing pentafluorophenyl group is 3：7-8：2.
3. the preparation method of double Biomimetic Polymers according to claim 1 or 2, which is characterized in that in the step (1)：
The vinyl monomer containing Phosphorylcholine group includes methylacryoyloxyethyl Phosphorylcholine；
The vinyl monomer containing pentafluorophenyl group includes methacrylic acid pentafluorophenyl esters.
4. according to the preparation method of the double Biomimetic Polymers of claim 1-3 any one of them, which is characterized in that the step
(1) in, the temperature for controlling the Raolical polymerizable is 60-80 DEG C.
5. according to the preparation method of the double Biomimetic Polymers of claim 1-4 any one of them, which is characterized in that the step
(1) further include the steps that reaction raw materials are added in organic solvent to carry out Raolical polymerizable, the organic solvent is four in
Hydrogen furans, and the mixed solution added with ethyl alcohol or methanol.
6. according to the preparation method of the double Biomimetic Polymers of claim 1-5 any one of them, which is characterized in that the step
(2) in, the mole of the dopamine is pentafluorophenyl group mole in the phosphoryl choline polymer containing pentafluorophenyl group
10-120%.
7. according to the preparation method of the double Biomimetic Polymers of claim 1-6 any one of them, which is characterized in that the step
(2) in, the polar solvent includes water, methanol or ethyl alcohol.
8. according to the preparation method of the double Biomimetic Polymers of claim 1-7 any one of them, which is characterized in that the step
(2) in, the temperature for controlling the graft reaction is 30-55 DEG C.
9. the double Biomimetic Polymers being prepared by claim 1-8 any one of them methods.
10. double Biomimetic Polymers described in claim 9 are used to carry out the purposes of material surface biocompatibility modification.
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