CN104744635A - Preparation method of di-bionic polymer - Google Patents
Preparation method of di-bionic polymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a di-bionic polymer. The preparation method comprises the following steps: I, preparing a phosphorylcholine polymer containing epoxy groups; and II, dissolving the phosphorylcholine polymer containing epoxy groups in a polar solvent to obtain a polymer solution; under protection of nitrogen, heating the polymer solution to 35-70 DEG C; then adding dopamine hydrochloride and an acid-binding agent into the polymer solution; carrying out grafting reaction under the insulating and stirring condition; after reaction, dialyzing the reaction product in a dialyzing bag by using an aqueous hydrochloric acid solution with the pH value of 3-4; and finally, freeze-drying the dialyzed reaction product to obtain the di-bionic polymer. The preparation method disclosed by the invention is simple in method, mild in condition and high in grafting rate of dopamine, the molar ratio of dopamine groups in the prepared di-bionic polymer is greater than 10%, and the di-bionic polymer is strong in adhesive force and hard to fall.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, be specifically related to the preparation method of a kind of pair of Biomimetic Polymers.
Background technology
Easy non-specific adsorption albumen when material is used in organism, activating complement molecule and immunity system, thus cause blood coagulation, immunity and inflammatory reaction, so that its performance significantly reduces, and even loses efficacy.This is due to the poor cause of Biocompatibility, and thus, Study on biocompatibility has become the matter of utmost importance in biomaterial research field.Material surface is the medium that material contacts with organism, and the electric charge, parent/hydrophobicity, chemical constitution, pattern etc. on surface are the important factors affecting interfacial interaction between material and organism, is the principal element determining that whether Biocompatibility is excellent.Therefore, the biocompatibility improving material surface is the key solving this problem in science.The material of good biocompatibility being incorporated into material surface modifying is the interaction improved between material and organism, improves the simple and effective approach of Biocompatibility.The biocompatibility modification of material surface is an eternal theme in biomaterial research field, has important academic significance and huge application prospect.
In recent years, being incorporated into material surface by having the endotheliocyte of good blood compatibility, albumin, heparin and polyoxyethylene glycol, can obviously improving its biocompatibility, particularly significantly improving its blood compatibility.But still there are some problems in these methods.Such as: the interaction of endotheliocyte and material surface is poor, anti-blood impact capacity not good, easily come off.Albumin and activity in vivo component, in material surface competitive adsorption, cause the albumin content being adsorbed on material surface to reduce, even sex change.Heparin facile hydrolysis, causes it active obviously to decline, so that induces the complication such as hemorrhage, thrombocytopenia.In fierce respiratory, polyoxyethylene glycol is oxidized because of superoxide anion and hydrogen peroxide, and also there is biological pollution in various degree on its surface.
Phosphorylcholine (phosphorylcholine, PC) be the terminal hydrophilic group forming cytolemma elementary cell Yelkin TTS, it is the outer functional group in the tunic of extracellular, simultaneously with positive and negative xenogenesis electric charge, there is ability and the hydrophilicity of stronger Bound moisture, the surface of this structure and composition and physiological environment interact and not only can not adsorb and depositing proteins, also can not cause platelet activation, cause the untoward reactions such as blood coagulation, have good biocompatibility.Research in recent years shows, adopts Phosphorylcholine group and polymkeric substance thereof to build at material surface and has imitating cell outer-layer membrane structure, significantly can improve the blood compatibility of material.
Physics coating comprises dip-coating, spin coating and drips the mode such as paintings, because it has the advantage of simple, the easy to operate and mild condition of technique, is the promising approach building imitating cell outer-layer membrane structure acquisition superior bio consistency surface.But the wetting ability of Phosphorylcholine group is comparatively strong, and the phosphoryl choline polymer coating that physics is coated in material surface is easily dissolved, degraded in the physiological environment of complexity, even comes off.Thus, need crosslinkable or covalent linkage group to be incorporated in phosphoryl choline polymer, after chemical reaction by this polymeric coating crosslinked or covalent bonding at material surface.This adds the difficulty of the synthesis of this kind of phosphoryl choline polymer and the requirement of application effects on surface undoubtedly, also makes the tediously long complexity of the treating processes of this technology.Therefore, simple, widely applicable surface modifying method is used in the urgent need to research and development.
Recently, Messersmith seminar of the U.S. will imitate bivalves (Mussel) attachment proteins composition Dopamine HCL (Dopamine) and be combined with PEG, give water-soluble polymers in the adhesion property of material surface excellence, obtain the stable coatings with good stable against biological contamination.Dopamine HCL group in this coating is except having the multiple non covalent bond effects such as pi-pi accumulation, also oxidizable polymerization formation adhesivity gathers Dopamine HCL (PDA), can produce water-fast strong adhesive attraction with the multiple base material comprising metal, glass and plastics.In addition, Dopamine HCL coating has the molecule of biological function by Michael addition or schiff base reaction grafting.The surface modification method that this imitative bivalves adheres to can make up the coating of current physics and have to pass through the limitation that complicated chemical treatment could obtain stable coatings, simplifies condition and the process of material surface modifying.
With the material modified surface of two Biomimetic Polymers containing cellulosa film component Phosphorylcholine and bivalves attachment proteins composition Dopamine HCL, Dopamine HCL side base in polymkeric substance can adhere to the surfaces of various materials comprising tetrafluoroethylene from the aqueous solution, Phosphorylcholine side base then forms imitating cell outer-layer membrane structure automatically at coatingsurface, significantly improves the biocompatibility of base material.This technology is that the biocompatibility of graphene oxide provides the possibility being worth exploring.But the phenolic hydroxyl group in Dopamine HCL monomer is the stopper of radical polymerization, thus protection phenolic hydroxyl group is the necessary process of this kind of monomer polymerization, is also the difficult point of Dopaminergics Macroscopic single crystal.For this reason, utilize amino and carboxyl reaction to be grafted to by Dopamine HCL on the phosphoryl choline polymer containing carboxyl, the protection process of phenolic hydroxyl group can be omitted.But the percentage of grafting of Dopamine HCL is only 4% in two Biomimetic Polymers prepared by this method, make this polymeric coating adhesive power be lower easily to come off.Although synthesized the high and controlled two Biomimetic Polymers of DOPAMINE CONTENT IN RABBIT by active ester monomer approach, this active ester monomer has needed in water-less environment preparation, and its separating-purifying is extremely difficult.
Summary of the invention
Technical problem to be solved by this invention is, for above-mentioned the deficiencies in the prior art, to provide the preparation method of a kind of pair of Biomimetic Polymers.The method is simple, mild condition, vinyl monomer containing Phosphorylcholine hydrophilic radical and the vinyl monomer containing epoxide group are passed through simple solution free radical polymerization by the method, the phosphoryl choline polymer of synthesis containing epoxide group, and polymkeric substance is mixed with dopamine hydrochloride under nitrogen protection, add a certain amount of acid binding agent again, carry out graft reaction at a certain temperature, to dialyse in acid condition hydrolysis after reaction terminates, two Biomimetic Polymers can be obtained, the percentage of grafting of Dopamine HCL is high, in two Biomimetic Polymers of preparation, the molar content of Dopamine HCL group is greater than 10%, the strong difficult drop-off of adhesive power.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of a kind of pair of Biomimetic Polymers, is characterized in that, comprises the following steps:
Step one, under nitrogen protection, carries out Raolical polymerizable by the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxide group, obtains the phosphoryl choline polymer containing epoxide group under the effect of initiator;
Step 2, be dissolved in polar solvent by described in step one containing the phosphoryl choline polymer of epoxide group, obtain polymers soln, under nitrogen protection, described polymers soln is heated to 35 DEG C ~ 70 DEG C, then in polymers soln, dopamine hydrochloride and acid binding agent is added, graft reaction is carried out under insulated and stirred condition, it is hemodialysis reaction product in the aqueous hydrochloric acid of 3 ~ 4 in pH value that reaction terminates rear dialysis tubing, finally by the reaction product lyophilize after dialysis, obtain two Biomimetic Polymers; The molar weight of described dopamine hydrochloride is 30% ~ 120% of the phosphoryl choline polymer epoxy group group molar weight containing epoxide group, and the molar weight of acid binding agent is 105% ~ 123% of dopamine hydrochloride molar weight.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, vinyl monomer described in step one is methacrylic monomer, acrylic monomer, methacryloyl amine monomer or acrylamide monomers.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, initiator described in step one is Diisopropyl azodicarboxylate.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, the mol ratio of the vinyl monomer containing Phosphorylcholine group described in step one and the vinyl monomer containing epoxide group is (0.42 ~ 9): 1.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, the temperature of Raolical polymerizable described in step one 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, is characterized in that, the solvent of Raolical polymerizable described in step one by methyl alcohol and tetrahydrofuran (THF) according to (6 ~ 8): the volume ratio of 1 mixes.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, polar solvent described in step 2 is water, methyl alcohol or ethanol.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, acid binding agent described in step 2 is triethylamine or pyridine.
The preparation method of a kind of pair of above-mentioned Biomimetic Polymers, is characterized in that, the time of graft reaction described in step 2 is 2h ~ 24h.
The present invention compared with prior art has the following advantages:
1, vinyl monomer containing Phosphorylcholine hydrophilic radical and the vinyl monomer containing epoxide group are passed through simple solution free radical polymerization by the present invention, the phosphoryl choline polymer of synthesis containing epoxide group, and polymkeric substance is mixed with dopamine hydrochloride under nitrogen protection, add a certain amount of acid binding agent again, carry out graft reaction at a certain temperature, to dialyse in acid condition hydrolysis after reaction terminates, two Biomimetic Polymers can be obtained, the percentage of grafting of Dopamine HCL is high, in two Biomimetic Polymers of preparation, the molar content of Dopamine HCL group is greater than 10%, the strong difficult drop-off of adhesive power.
2, simple, the mild condition of preparation method of the present invention, provides a kind of new approach for obtaining two Biomimetic Polymers.
3, the two Biomimetic Polymers embedded material in vivo adopting the inventive method to prepare, organizational project, the field such as medicament slow release and biosensor has broad application prospects.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of two Biomimetic Polymers of the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of two Biomimetic Polymers prepared by the embodiment of the present invention 1.
Embodiment
Embodiment 1
The present embodiment comprises the following steps:
Step one, take 5mmol 2-methacryloxyethyl Phosphorylcholine and 5mmol glycidyl methacrylate, the mixing solutions obtaining monomer is mixed by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 70 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, adds initiator solution and continues reaction 24h, and after reaction terminates, concentration of reaction solution is the dialysis tubing dialysis of 6000 ~ 8000D with molecular weight cut-off; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 7:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 57.7%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL methyl alcohol containing the phosphoryl choline polymer of epoxide group described in 0.38mmol step one
2protection; under 60 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.26mmol dopamine hydrochloride and 0.32mmol triethylamine; insulated and stirred reaction 24h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 3 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic (see Fig. 2) that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak, shows do not have residual monomer in resulting polymers, and successfully synthesize this polymkeric substance, with 3.28ppm place for-N at 5ppm ~ 6.5ppm place
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 25.9%.
Embodiment 2
The present embodiment comprises the following steps:
Step one, take 7mmol acryloyl-oxyethyl Phosphorylcholine and 3mmol glycidyl acrylate, mix the mixing solutions obtaining monomer by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 60 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, add initiator solution and continue reaction 24h, after reaction terminates, concentration of reaction solution, the reaction solution after concentrating with the dialysis tubing dialysis that molecular weight cut-off is 6000 ~ 8000D; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 6:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 39.2%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL ethanol containing the phosphoryl choline polymer of epoxide group described in 0.40mmol step one
2protection; under 40 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.188mmol dopamine hydrochloride and 0.20mmol triethylamine; insulated and stirred reaction 24h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 4 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak at 5ppm ~ 6.5ppm place, shows do not have residual monomer in resulting polymers, and successfully synthesizes this polymkeric substance, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 21.3%.
Embodiment 3
The present embodiment comprises the following steps:
Step one, take 6mmol 2-Methacrylamide ethylphosphocholine and 4mmol glycidyl acrylate, mix the mixing solutions obtaining monomer by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 80 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, adds initiator solution and continues reaction 12h, and after reaction terminates, concentration of reaction solution is the dialysis tubing dialysis of 6000 ~ 8000D with molecular weight cut-off; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 8:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 48.1%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL methyl alcohol containing the phosphoryl choline polymer of epoxide group described in 0.5mmol step one
2protection; under 50 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.072mmol dopamine hydrochloride and 0.079mmol triethylamine; insulated and stirred reaction 12h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 3.5 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak at 5ppm ~ 6.5ppm place, shows do not have residual monomer in resulting polymers, and successfully synthesizes this polymkeric substance, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 23.7%.
Embodiment 4
The present embodiment comprises the following steps:
Step one, take 4mmol 2-methacryloxyethyl Phosphorylcholine and 6mmol glycidyl methacrylate, the mixing solutions obtaining monomer is mixed by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 70 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, adds initiator solution and continues reaction 20h, and after reaction terminates, concentration of reaction solution is the dialysis tubing dialysis of 6000 ~ 8000D with molecular weight cut-off; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 7:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 68.1%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL methyl alcohol containing the phosphoryl choline polymer of epoxide group described in 0.3mmol step one
2protection; under 35 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.2mmol dopamine hydrochloride and 0.24mmol triethylamine; insulated and stirred reaction 24h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 3 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak at 5ppm ~ 6.5ppm place, shows do not have residual monomer in resulting polymers, and successfully synthesizes this polymkeric substance, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 27.4%.
Embodiment 5
The present embodiment comprises the following steps:
Step one, take 3mmol 2-methacryloxyethyl Phosphorylcholine and 7mmol glycidyl methacrylate, the mixing solutions obtaining monomer is mixed by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 60 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, adds initiator solution and continues reaction 12h, and after reaction terminates, concentration of reaction solution is the dialysis tubing dialysis of 6000 ~ 8000D with molecular weight cut-off; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 7:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 72.5%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL methyl alcohol containing the phosphoryl choline polymer of epoxide group described in 0.3mmol step one
2protection; under 70 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.26mmol dopamine hydrochloride and 0.28mmol pyridine; insulated and stirred reaction 2h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 4 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak at 5ppm ~ 6.5ppm place, shows do not have residual monomer in resulting polymers, and successfully synthesizes this polymkeric substance, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 28.3%.
Embodiment 6
The present embodiment comprises the following steps:
Step one, take 9mmol 2-methacryloxyethyl Phosphorylcholine and 1mmol glycidyl methacrylate, the mixing solutions obtaining monomer is mixed by dissolution with solvents, 0.1mmol Diisopropyl azodicarboxylate tetrahydrofuran (THF) is dissolved and obtains initiator solution, at N
2protection, under 60 DEG C of agitation conditions, adds the mixing solutions of monomer in three-necked bottle, after preheating 30min, add initiator solution and continue reaction 12h, after reaction terminates, concentration of reaction solution, the reaction solution after concentrating with the dialysis tubing dialysis that molecular weight cut-off is 6000 ~ 8000D; Finally, by the sample lyophilize at-50 DEG C after dialysis, obtain the phosphoryl choline polymer containing epoxide group; Described solvent is mixed according to the volume ratio of 7:1 by methyl alcohol and tetrahydrofuran (THF); Nuclear-magnetism test result shows, this polymkeric substance epoxy group group molar content is about 15.4%;
Step 2, obtain polymers soln, at N by being dissolved in 20mL methyl alcohol containing the phosphoryl choline polymer of epoxide group described in 0.5mmol step one
2protection; under 70 DEG C of agitation conditions; in three-necked bottle, add described polymers soln, preheating 30min, then add 0.08mmol dopamine hydrochloride and 0.084mmol pyridine; insulated and stirred reaction 10h; after reaction terminates, concentration of reaction solution is that the dialysis tubing of 6000 ~ 8000D is the reaction solution after concentrating of dialysing in the aqueous hydrochloric acid of 4 in pH value with molecular weight cut-off; by the sample lyophilize at-50 DEG C after dialysis, obtain two Biomimetic Polymers.
By 400MHz nuclear magnetic resonance analyser with D
2o is the proton magnetic that two Biomimetic Polymers prepared by the present embodiment tested by solvent, has no out peak at 5ppm ~ 6.5ppm place, shows do not have residual monomer in resulting polymers, and successfully synthesizes this polymkeric substance, with 3.28ppm place for-N
+(CH
3)
3characteristic peak, 0.9ppm ~ 2.2ppm place is the peak of methylene radical and pendant methyl on main chain, and 6.8ppm ~ 7.2ppm place is the peak calculating polymkeric substance composition of the phenyl ring on Dopamine HCL group, and in this pair of Biomimetic Polymers, the molar content of Dopamine HCL group is about 10.8%.
In two Biomimetic Polymers prepared by the embodiment of the present invention 1 to embodiment 6, the molar content of Dopamine HCL group is all greater than 10%, is enough to adhesion material surface.Stable for proving that it adheres to further, two Biomimetic Polymers embodiment 1 to embodiment 6 prepared are coated on matrix (glass or chitosan) surface respectively, then soak with the sodium hydroxide solution that pH value is 9 the matrix surface 6h being coated with two Biomimetic Polymers, the matrix that surface attachment has two Biomimetic Polymers is obtained after drying, the matrix of two Biomimetic Polymers is finally had by distilled water flushing surface attachment, the surface attachment measured before and after distilled water flushing has the contact angle of the matrix of two Biomimetic Polymers, before and after distilled water flushing, contact angle is unchanged, illustrate that two Biomimetic Polymers prepared by the present invention are stable and adhere to matrix surface.
The above; it is only preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (9)
1. a preparation method for two Biomimetic Polymers, is characterized in that, comprise the following steps:
Step one, under nitrogen protection, carries out Raolical polymerizable by the vinyl monomer containing Phosphorylcholine group and the vinyl monomer containing epoxide group, obtains the phosphoryl choline polymer containing epoxide group under the effect of initiator;
Step 2, be dissolved in polar solvent by described in step one containing the phosphoryl choline polymer of epoxide group, obtain polymers soln, under nitrogen protection, described polymers soln is heated to 35 DEG C ~ 70 DEG C, then in polymers soln, dopamine hydrochloride and acid binding agent is added, graft reaction is carried out under insulated and stirred condition, it is hemodialysis reaction product in the aqueous hydrochloric acid of 3 ~ 4 in pH value that reaction terminates rear dialysis tubing, finally by the reaction product lyophilize after dialysis, obtain two Biomimetic Polymers; The molar weight of described dopamine hydrochloride is 30% ~ 120% of the phosphoryl choline polymer epoxy group group molar weight containing epoxide group, and the molar weight of acid binding agent is 105% ~ 123% of dopamine hydrochloride molar weight.
2. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, vinyl monomer described in step one is methacrylic monomer, acrylic monomer, methacryloyl amine monomer or acrylamide monomers.
3. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, initiator described in step one is Diisopropyl azodicarboxylate.
4. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, the mol ratio of the vinyl monomer containing Phosphorylcholine group described in step one and the vinyl monomer containing epoxide group is (0.42 ~ 9): 1.
5. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, the temperature of Raolical polymerizable described in step one is 60 DEG C ~ 80 DEG C, and the time is 12h ~ 24h.
6. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, the solvent of Raolical polymerizable described in step one by methyl alcohol and tetrahydrofuran (THF) according to (6 ~ 8): the volume ratio of 1 mixes.
7. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, polar solvent described in step 2 is water, methyl alcohol or ethanol.
8. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, acid binding agent described in step 2 is triethylamine or pyridine.
9. the preparation method of a kind of pair of Biomimetic Polymers according to claim 1, is characterized in that, the time of graft reaction described in step 2 is 2h ~ 24h.
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| CN106832382A (en) * | 2016-11-07 | 2017-06-13 | 西安科技大学 | A kind of synthesis of double bionical dopamine Phosphorylcholine materials and its painting method |
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| CN108659168A (en) * | 2018-05-30 | 2018-10-16 | 西安文理学院 | A kind of double Biomimetic Polymers and the preparation method and application thereof |
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| CN109796616A (en) * | 2019-01-11 | 2019-05-24 | 西北大学 | The method and application of a kind of Biomimetic Polymers and the double Biomimetic Polymers coatings of production durability |
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| 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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