CN104744635B - A kind of preparation method of pair of Biomimetic Polymers - Google Patents
A kind of preparation method of pair of Biomimetic Polymers Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of pair of Biomimetic Polymers, comprise the following steps：First, the phosphoryl choline polymer containing epoxide group is prepared；2nd, the phosphoryl choline polymer containing epoxide group is dissolved in polar solvent; obtain polymer solution; under nitrogen protection; the polymer solution is heated to 35 DEG C~70 DEG C; then Dopamine hydrochloride and acid binding agent are added into polymer solution, graft reaction is carried out under the conditions of insulated and stirred, bag filter hemodialysis reaction product in pH value is 3~4 aqueous hydrochloric acid solution is used in reaction after terminating; finally the reaction product after dialysis is freeze-dried, double Biomimetic Polymers are obtained.The preparation method of the present invention is simple, mild condition, and the grafting rate of dopamine is high, and the molar content of DOPA amine groups is more than 10% in double Biomimetic Polymers of preparation, and adhesion is difficult for drop-off by force.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to a kind of double bionical
The preparation method of polymer.
Background technology
Material is used for easy non-specific adsorption albumen, activating complement molecule and immune system when in organism, so as to cause
Blood coagulation, immune and inflammatory reaction, so that its performance is significantly reduced, or even failure.This is due to that Biocompatibility is poor
Reason, thus, Study on biocompatibility turns into the matter of utmost importance in biomaterial research field.Material surface is material and life
The medium of object contact, electric charge, parent/hydrophobicity, chemical composition, the pattern on surface etc. are interfaces between influence material and organism
The key factor of interaction, is the principal element for determining whether Biocompatibility is excellent.Therefore, material surface is improved
Biocompatibility is the key for solving this problem in science.The material of good biocompatibility is incorporated into material surface modifying is
Improve the interaction between material and organism, improve the simple and effective approach of Biocompatibility.Material surface
It is an eternal theme in biomaterial research field that biocompatibility, which is modified, with important academic significance and it is huge should
Use prospect.
In recent years, the endothelial cell with good blood compatibility, albumin, heparin and polyethylene glycol are incorporated into material
Surface, can be obviously improved its biocompatibility, particularly significantly improve its blood compatibility.But, these methods are still deposited
In some problems.For example：The interaction of endothelial cell and material surface is poor, and anti-blood impact capacity is not good, easy to fall off.In vain
Albumen, in material surface competitive Adsorption, causes absorption to be reduced in the albumin content of material surface, even with activity in vivo component
Denaturation.Heparin facile hydrolysis, causes its activity to be decreased obviously, so that the complication such as induction bleeding, thrombopenia.Fiercely exhaling
During suction, polyethylene glycol is oxidized because of superoxide anion and hydrogen peroxide, and also there is different degrees of biological pollution on its surface.
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, surface and the physiological environment interaction of this structure and composition will not only be adsorbed and depositing proteins, will not also be triggered
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 are built in material surface has imitating cell outer-layer membrane structure, can significantly improve the blood phase of material
Capacitive.
Physics coating includes the modes such as dip-coating, spin coating and drop coating, because there is technique to be simple and convenient to operate and mild condition for it
Advantage, be to build the promising approach that imitating cell outer-layer membrane structure obtains superior bio compatibility surface.However, Phosphorylcholine base
The hydrophily of group is stronger, and physics is coated in the phosphoryl choline polymer coating of material surface and easily sent out in complicated physiological environment
Raw dissolving, degraded, or even come off.It is then desired to which cross-linking or covalent bond group is incorporated into phosphoryl choline polymer, pass through
Chemical reaction is crosslinked the polymer coating or covalent bonding is in material surface.This undoubtedly adds this kind of phosphoryl choline polymer
Synthesis and application also cause the tediously long complexity of processing procedure of the technology to the difficulty of surface requirements.Therefore, in the urgent need to research is opened
Hair uses simple, widely applicable surface modifying method.
Recently, Messersmith seminars in the U.S. are by imitative bivalves (Mussel) attachment proteins composition dopamine
(Dopamine) combined with PEG, assign water-soluble polymer in the excellent adhesion property of material surface, obtained with good anti-
The stable coatings of biological pollution.DOPA amine groups in the coating are in addition to a variety of non-covalent bond effects such as pi-pi accumulation, also
Oxidizable polymerization forms adhesiveness poly-dopamine (PDA), can be produced with a variety of base materials including metal, glass and plastics resistance to
The strong adhesive attraction of water.In addition, dopamine coating can have biological function by Michael's addition or schiff base reaction grafting
Molecule.The surface modification method of this imitative bivalves adhesion can make up current physics coating and have to pass through the chemical treatment of complexity
The limitation of stable coatings can be obtained, simplifies the condition and process of material surface modifying.
Changed with double Biomimetic Polymers containing cellulosa film component Phosphorylcholine and bivalves attachment proteins composition dopamine
Dopamine side base in property material surface, polymer is can be adhered from the aqueous solution to the multiple material including polytetrafluoroethylene (PTFE)
Surface, Phosphorylcholine side base then automatically forms imitating cell outer-layer membrane structure in coating surface, significantly improves the life of base material
Thing compatibility.The technology provides for the biocompatibility of graphene oxide is worth the possibility of exploration.However, DOPA amine monomers
In phenolic hydroxyl group be radical polymerization polymerization inhibitor, thus protection phenolic hydroxyl group is the necessary process of this kind of monomer polymerization, is also many
The difficult point of bar amine polymer synthesis.Therefore, dopamine to be grafted to the phosphinylidyne courage containing carboxyl using amino and carboxyl reaction
On alkali polymer, the protection process of phenolic hydroxyl group can be omitted.But the grafting of dopamine in double Biomimetic Polymers prepared by this method
Rate is only 4% so that the polymer coating adhesion is relatively low easy to fall off.Although having synthesized dopamine with active ester monomer approach to contain
The high and controllable double Biomimetic Polymers of amount, but active ester monomer needs are in water-less environment preparation, and also its separating-purifying is extremely
It is difficult.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of double bionical polymerizations for above-mentioned the deficiencies in the prior art
The preparation method of thing.This method is simple, mild condition, this method by the vinyl monomer containing Phosphorylcholine hydrophilic radical and
Vinyl monomer containing epoxide group is gathered by simple solution free radical polymerization, Phosphorylcholine of the synthesis containing epoxide group
Compound, and polymer is mixed with Dopamine hydrochloride under nitrogen protection, a certain amount of acid binding agent is added, at a certain temperature
Carry out graft reaction, dialysis hydrolysis in acid condition after reaction terminates, you can obtain double Biomimetic Polymers, the grafting of dopamine
Rate is high, and the molar content of DOPA amine groups is more than 10% in double Biomimetic Polymers of preparation, and adhesion is difficult for drop-off by force.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of preparation method of pair of Biomimetic Polymers,
It is characterised in that it includes following steps：
Step 1: under nitrogen protection, by the vinyl monomer containing Phosphorylcholine group and the second containing epoxide group
Alkenyl monomer carries out Raolical polymerizable in the presence of initiator, obtains the phosphoryl choline polymer containing epoxide group；
Step 2: the phosphoryl choline polymer containing epoxide group described in step one is dissolved in polar solvent, gathered
Polymer solution, under nitrogen protection, 35 DEG C~70 DEG C is heated to by the polymer solution, is then added into polymer solution
Dopamine hydrochloride and acid binding agent, carry out graft reaction under the conditions of insulated and stirred, reaction terminate after with bag filter pH value be 3~
Reaction product after dialysis, is finally freeze-dried by hemodialysis reaction product in 4 aqueous hydrochloric acid solution, obtains double Biomimetic Polymers；
The mole of the Dopamine hydrochloride for the phosphoryl choline polymer epoxide epoxy group group mole containing epoxide group 30%~
120%, the mole of acid binding agent is the 105%~123% of Dopamine hydrochloride mole.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that vinyl monomer is described in step one
Methacrylic monomer, acrylic monomer, methacryl amine monomer or acrylamide monomers.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that initiator described in step one is azo
Bis-isobutyronitrile.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that contain Phosphorylcholine described in step one
The mol ratio of the vinyl monomer of group and vinyl monomer containing epoxide group is (0.42~9):1.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that radical polymerization is anti-described in step one
The temperature answered is 60 DEG C~80 DEG C, and the time is 12h~24h.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that radical polymerization is anti-described in step one
The solvent answered is by methanol and tetrahydrofuran according to (6~8):1 volume ratio is mixed.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that polar solvent is described in step 2
Water, methanol or ethanol.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that acid binding agent described in step 2 is three second
Amine or pyridine.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, it is characterised in that graft reaction described in step 2 when
Between be 2h~24h.
The present invention has advantages below compared with prior art：
1st, the vinyl list of the invention by the vinyl monomer containing Phosphorylcholine hydrophilic radical and containing epoxide group
Body synthesizes the phosphoryl choline polymer containing epoxide group by simple solution free radical polymerization, and by polymer in nitrogen
Protection is lower to be mixed with Dopamine hydrochloride, adds a certain amount of acid binding agent, graft reaction is carried out at a certain temperature, reaction terminates
Dialysis hydrolysis in acid condition afterwards, you can obtain double Biomimetic Polymers, the grafting rate of dopamine is high, double bionical polymerizations of preparation
The molar content of DOPA amine groups is more than 10% in thing, and adhesion is difficult for drop-off by force.
2nd, preparation method of the invention is simple, mild condition, and a kind of new approach is provided to obtain double Biomimetic Polymers.
3rd, the double Biomimetic Polymers prepared using the inventive method are implanted into material in vivo, organizational project, medicament slow release and
The fields such as biology 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 synthetic route chart of double Biomimetic Polymers of the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of double Biomimetic Polymers prepared by the embodiment of the present invention 1.
Embodiment
Embodiment 1
The present embodiment comprises the following steps：
Step 1: weighing 5mmol 2- methacryloxyethyls Phosphorylcholines and 5mmol Glycidyl methacrylates are sweet
Grease, dissolves the well mixed mixed solution for obtaining monomer with solvent, 0.1mmol azodiisobutyronitrile tetrahydrofurans is dissolved
Initiator solution is obtained, in N2Under protection, 70 DEG C of stirring conditions, the mixed solution of monomer is added into three-necked bottle, 30min is preheated
Afterwards, add initiator solution to continue to react 24h, after reaction terminates, concentration of reaction solution is 6000~8000D with molecular cut off
Bag filter dialysis；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains the Phosphorylcholine containing epoxide group and gather
Compound；The solvent is by methanol and tetrahydrofuran according to 7:1 volume ratio is mixed；Nuclear-magnetism test result shows, the polymerization
Thing epoxide epoxy group group molar content is about 57.7%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.38mmol steps one is dissolved in 20mL methanol
Polymer solution is obtained, in N2Under protection, 60 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.26mmol Dopamine hydrochlorides and 0.32mmol triethylamines, insulated and stirred reaction 24h is reacted after terminating, dense
Contracting reaction solution, the bag filter for being 6000~8000D with molecular cut off is dialysed in the aqueous hydrochloric acid solution that pH value is 3 after concentration
Reaction solution, the sample after dialysis is freeze-dried at -50 DEG C, obtains double Biomimetic Polymers.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers
(see Fig. 2), has no appearance at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesize this
Polymer, using at 3.28ppm as-N+(CH3)3It is methylene and pendant methyl on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at peak, 6.8ppm~7.2ppm for the phenyl ring in DOPA amine groups calculates many in polymer composition, this pair of Biomimetic Polymers
The molar content of bar amine groups is about 25.9%.
Embodiment 2
The present embodiment comprises the following steps：
Step 1: weighing 7mmol acryloyl-oxyethyls Phosphorylcholine and 3mmol glycidyl acrylates, solvent is used
The well mixed mixed solution for obtaining monomer of dissolving, initiator is obtained by the dissolving of 0.1mmol azodiisobutyronitriles tetrahydrofuran
Solution, in N2Under protection, 60 DEG C of stirring conditions, added into three-necked bottle after the mixed solution of monomer, preheating 30min, addition is drawn
Send out agent solution to continue to react 24h, after reaction terminates, concentration of reaction solution is saturating for 6000~8000D bag filter with molecular cut off
Reaction solution after analysis concentration；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains the phosphinylidyne courage containing epoxide group
Alkali polymer；The solvent is by methanol and tetrahydrofuran according to 6:1 volume ratio is mixed；Nuclear-magnetism test result shows, is somebody's turn to do
Polymer epoxide epoxy group group molar content is about 39.2%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.40mmol steps one is dissolved in 20mL ethanol
Polymer solution is obtained, in N2Under protection, 40 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.188mmol Dopamine hydrochlorides and 0.20mmol triethylamines, insulated and stirred reaction 24h is reacted after terminating, dense
Contracting reaction solution, the bag filter for being 6000~8000D with molecular cut off is dialysed in the aqueous hydrochloric acid solution that pH value is 4 after concentration
Reaction solution, the sample after dialysis is freeze-dried at -50 DEG C, obtains double Biomimetic Polymers.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers,
Appearance is had no at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3It is methylene and the peak of pendant methyl, 6.8ppm on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at~7.2ppm for the phenyl ring in DOPA amine groups calculates DOPA amine groups in polymer composition, this pair of Biomimetic Polymers
Molar content is about 21.3%.
Embodiment 3
The present embodiment comprises the following steps：
Step 1: weighing 6mmol 2- Methacrylamides ethylphosphocholines and 4mmol glycidyl acrylates, use
The well mixed mixed solution for obtaining monomer of solvent dissolving, the dissolving of 0.1mmol azodiisobutyronitriles tetrahydrofuran is drawn
Agent solution is sent out, in N2Under protection, 80 DEG C of stirring conditions, added into three-necked bottle after the mixed solution of monomer, preheating 30min, plus
Enter initiator solution to continue to react 12h, after reaction terminates, concentration of reaction solution, with the dialysis that molecular cut off is 6000~8000D
Bag dialysis；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxide group；Institute
Solvent is stated by methanol and tetrahydrofuran according to 8:1 volume ratio is mixed；Nuclear-magnetism test result shows, epoxy in the polymer
Group molar content is about 48.1%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.5mmol steps one is dissolved in 20mL methanol
Polymer solution is obtained, in N2Under protection, 50 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.072mmol Dopamine hydrochlorides and 0.079mmol triethylamines, and insulated and stirred reaction 12h is reacted after terminating,
Concentration of reaction solution, the bag filter for being 6000~8000D with molecular cut off is dialysed concentration in the aqueous hydrochloric acid solution that pH value is 3.5
Reaction solution afterwards, the sample after dialysis is freeze-dried at -50 DEG C, obtains double Biomimetic Polymers.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers,
Appearance is had no at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3It is methylene and the peak of pendant methyl, 6.8ppm on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at~7.2ppm for the phenyl ring in DOPA amine groups calculates DOPA amine groups in polymer composition, this pair of Biomimetic Polymers
Molar content is about 23.7%.
Embodiment 4
The present embodiment comprises the following steps：
Step 1: weighing 4mmol 2- methacryloxyethyls Phosphorylcholines and 6mmol Glycidyl methacrylates are sweet
Grease, dissolves the well mixed mixed solution for obtaining monomer with solvent, 0.1mmol azodiisobutyronitrile tetrahydrofurans is dissolved
Initiator solution is obtained, in N2Under protection, 70 DEG C of stirring conditions, the mixed solution of monomer is added into three-necked bottle, 30min is preheated
Afterwards, add initiator solution to continue to react 20h, after reaction terminates, concentration of reaction solution is 6000~8000D with molecular cut off
Bag filter dialysis；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains the Phosphorylcholine containing epoxide group and gather
Compound；The solvent is by methanol and tetrahydrofuran according to 7:1 volume ratio is mixed；Nuclear-magnetism test result shows, the polymerization
Thing epoxide epoxy group group molar content is about 68.1%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.3mmol steps one is dissolved in 20mL methanol
Polymer solution is obtained, in N2Under protection, 35 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.2mmol Dopamine hydrochlorides and 0.24mmol triethylamines, and insulated and stirred reaction 24h after reaction terminates, is concentrated
Reaction solution, the bag filter for being 6000~8000D with molecular cut off dialysed in the aqueous hydrochloric acid solution that pH value is 3 concentration after it is anti-
Liquid is answered, the sample after dialysis is freeze-dried at -50 DEG C, double Biomimetic Polymers are obtained.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers,
Appearance is had no at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3It is methylene and the peak of pendant methyl, 6.8ppm on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at~7.2ppm for the phenyl ring in DOPA amine groups calculates DOPA amine groups in polymer composition, this pair of Biomimetic Polymers
Molar content is about 27.4%.
Embodiment 5
The present embodiment comprises the following steps：
Step 1: weighing 3mmol 2- methacryloxyethyls Phosphorylcholines and 7mmol Glycidyl methacrylates are sweet
Grease, dissolves the well mixed mixed solution for obtaining monomer with solvent, 0.1mmol azodiisobutyronitrile tetrahydrofurans is dissolved
Initiator solution is obtained, in N2Under protection, 60 DEG C of stirring conditions, the mixed solution of monomer is added into three-necked bottle, 30min is preheated
Afterwards, add initiator solution to continue to react 12h, after reaction terminates, concentration of reaction solution is 6000~8000D with molecular cut off
Bag filter dialysis；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains the Phosphorylcholine containing epoxide group and gather
Compound；The solvent is by methanol and tetrahydrofuran according to 7:1 volume ratio is mixed；Nuclear-magnetism test result shows, the polymerization
Thing epoxide epoxy group group molar content is about 72.5%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.3mmol steps one is dissolved in 20mL methanol
Polymer solution is obtained, in N2Under protection, 70 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.26mmol Dopamine hydrochlorides and 0.28mmol pyridines, and insulated and stirred reaction 2h after reaction terminates, is concentrated anti-
Answer liquid, the bag filter for being 6000~8000D with molecular cut off dialysed in the aqueous hydrochloric acid solution that pH value is 4 concentration after reaction
Liquid, the sample after dialysis is freeze-dried at -50 DEG C, obtains double Biomimetic Polymers.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers,
Appearance is had no at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3It is methylene and the peak of pendant methyl, 6.8ppm on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at~7.2ppm for the phenyl ring in DOPA amine groups calculates DOPA amine groups in polymer composition, this pair of Biomimetic Polymers
Molar content is about 28.3%.
Embodiment 6
The present embodiment comprises the following steps：
Step 1: weighing 9mmol 2- methacryloxyethyls Phosphorylcholines and 1mmol Glycidyl methacrylates are sweet
Grease, dissolves the well mixed mixed solution for obtaining monomer with solvent, 0.1mmol azodiisobutyronitrile tetrahydrofurans is dissolved
Initiator solution is obtained, in N2Under protection, 60 DEG C of stirring conditions, the mixed solution of monomer is added into three-necked bottle, 30min is preheated
Afterwards, add initiator solution to continue to react 12h, after reaction terminates, concentration of reaction solution is 6000~8000D with molecular cut off
Bag filter dialysis concentration after reaction solution；Finally, the sample after dialysis is freeze-dried at -50 DEG C, obtains containing epoxy radicals
The phosphoryl choline polymer of group；The solvent is by methanol and tetrahydrofuran according to 7:1 volume ratio is mixed；Nuclear-magnetism test knot
Fruit shows that the polymer epoxide epoxy group group molar content is about 15.4%；
Step 2: the phosphoryl choline polymer containing epoxide group described in 0.5mmol steps one is dissolved in 20mL methanol
Polymer solution is obtained, in N2Under protection, 70 DEG C of stirring conditions, the polymer solution is added into three-necked bottle, is preheated
30min, adds 0.08mmol Dopamine hydrochlorides and 0.084mmol pyridines, and insulated and stirred reaction 10h after reaction terminates, is concentrated
Reaction solution, the bag filter for being 6000~8000D with molecular cut off dialysed in the aqueous hydrochloric acid solution that pH value is 4 concentration after it is anti-
Liquid is answered, the sample after dialysis is freeze-dried at -50 DEG C, double Biomimetic Polymers are obtained.
With 400MHz NMRs with D2O is the proton magnetic that solvent tests manufactured in the present embodiment pair of Biomimetic Polymers,
Appearance is had no at 5ppm~6.5ppm, shows do not have residual monomer in resulting polymers, and successfully synthesizes the polymer, with
It is-N at 3.28ppm+(CH3)3It is methylene and the peak of pendant methyl, 6.8ppm on main chain at characteristic peak, 0.9ppm~2.2ppm
Peak at~7.2ppm for the phenyl ring in DOPA amine groups calculates DOPA amine groups in polymer composition, this pair of Biomimetic Polymers
Molar content is about 10.8%.
The molar content of DOPA amine groups is all higher than in double Biomimetic Polymers that the embodiment of the present invention 1 is prepared to embodiment 6
10%, it is sufficient to adhesion material surface.Further to prove that its adhesion is stable, double bionical gather prepared by embodiment 1 to embodiment 6
Compound is respectively coated in matrix (glass or chitosan) surface, is then coated with the sodium hydroxide solution immersion that pH value is 9 double
The matrix surface 6h of Biomimetic Polymers, obtaining surface attachment after drying has the matrix of double Biomimetic Polymers, is finally rushed with distilled water
Washing surface attachment has a matrix of double Biomimetic Polymers, and determining the surface attachment before and after distilled water flushing has the base of double Biomimetic Polymers
Contact angle is unchanged before and after the contact angle of body, distilled water flushing, illustrates that double Biomimetic Polymers stabilization prepared by the present invention is adhered to
Matrix surface.
It is described above, only it is presently preferred embodiments of the present invention, any limitation is not done to the present invention, it is every according to invention skill
Any simple modification, change and 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 (7)
1. the preparation method of a kind of pair of Biomimetic Polymers, it is characterised in that comprise the following steps：
Step 1: under nitrogen protection, by the vinyl monomer containing Phosphorylcholine group and the vinyl containing epoxide group
Monomer carries out Raolical polymerizable in the presence of initiator, obtains the phosphoryl choline polymer containing epoxide group；It is described to contain
The mol ratio for having the vinyl monomer of Phosphorylcholine group and the vinyl monomer containing epoxide group is (0.42~9):1；Step
The temperature of Raolical polymerizable described in rapid one is 60 DEG C~80 DEG C, and the time is 12h~24h；
Step 2: the phosphoryl choline polymer containing epoxide group described in step one is dissolved in polar solvent, polymer is obtained
Solution, the polar solvent is water, methanol or ethanol, under nitrogen protection, by the polymer solution be heated to 35 DEG C~
70 DEG C, Dopamine hydrochloride and acid binding agent are then added into polymer solution, graft reaction is carried out under the conditions of insulated and stirred, instead
Bag filter hemodialysis reaction product in pH value is 3~4 aqueous hydrochloric acid solution is used after should terminating, finally by the reaction product after dialysis
Freeze-drying, obtains double Biomimetic Polymers；The mole of the Dopamine hydrochloride is the phosphoryl choline polymer containing epoxide group
The 30%~120% of epoxide epoxy group group mole, the mole of acid binding agent is the 105%~123% of Dopamine hydrochloride mole.
2. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that second described in step one
Alkenyl monomer is methacrylic monomer, acrylic monomer, methacryl amine monomer or acrylamide monomers.
3. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that draw described in step one
Hair agent is azodiisobutyronitrile.
4. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that described in step one certainly
By the solvent of base polymerisation by methanol and tetrahydrofuran according to (6~8):1 volume ratio is mixed.
5. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that pole described in step 2
Property solvent is water, methanol or ethanol.
6. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that tied up described in step 2
Sour agent is triethylamine or pyridine.
7. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, it is characterised in that connect described in step 2
The time of branch reaction is 2h~24h.
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| CN105288731B (en) * | 2015-11-16 | 2018-02-09 | 西安科技大学 | A kind of method that epoxy radicals prepares bionic coating with sulfydryl crosslinking |
| CN105237790B (en) * | 2015-11-16 | 2018-02-09 | 西安科技大学 | A kind of preparation method of double bionic coatings |
| CN106832382B (en) * | 2016-11-07 | 2020-11-13 | 西安科技大学 | Coating method of double-bionic dopamine phosphorylcholine substance |
| CN106866883B (en) * | 2017-03-01 | 2019-02-01 | 西安科技大学 | A method of the double Biomimetic Polymers of synthesis are reacted with amino based on aldehyde radical |
| CN108659168B (en) * | 2018-05-30 | 2020-12-11 | 西安文理学院 | Double-bionic polymer and preparation method and application thereof |
| CN108794794B (en) * | 2018-05-30 | 2021-02-26 | 西安文理学院 | Method for modifying surface biocompatibility of material and bionic coating prepared by method |
| CN109796616B (en) * | 2019-01-11 | 2020-04-10 | 西北大学 | Bionic polymer, method for manufacturing durable double-bionic polymer coating and application |
| CN111440653B (en) * | 2020-04-17 | 2021-11-30 | 清华大学 | Application of polydopamine nanoparticles in water-based lubricating fluid |
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| CN100415785C (en) * | 2006-08-25 | 2008-09-03 | 西北大学 | Copolymer of imitating structure of cell membrane, prepartion method and application |
| US20090112239A1 (en) * | 2007-10-31 | 2009-04-30 | Specialized Vascular Technologies, Inc. | Sticky dilatation balloon and methods of using |
| CN102887976B (en) * | 2011-07-21 | 2015-02-18 | 西北大学 | Imitation mussel attachment protein and cell membrane structure copolymer and preparation method and application thereof |
| CN102796224A (en) * | 2012-08-01 | 2012-11-28 | 刘丽平 | Multifunctional bionic polymer, its preparation method and application |
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