CN106905554A - A kind of phosphoryl choline polymer containing amino and the method for glutaraldehyde bionic coating density - Google Patents
A kind of phosphoryl choline polymer containing amino and the method for glutaraldehyde bionic coating density Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
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Abstract
The present invention is a kind of phosphoryl choline polymer containing amino and the method for glutaraldehyde bionic coating density.Vinyl monomer containing amphion Phosphorylcholine group, the vinyl monomer containing amino are passed through simple solution free radical polymerization by the present invention, phosphoryl choline polymer of the synthesis containing amino, and it is dissolved in polar solvent with glutaraldehyde is well mixed, being coated in needs modified material surface through treatment, then it is grafted the vinyl monomer of amphion Phosphorylcholine group, you can obtain surface Phosphorylcholine density imitating cell outer-layer membrane structure coating high.This preparation method is simple, mild condition, and a kind of new approach is provided to improve the excellent coating surface of coating surface Phosphorylcholine density acquisition blood compatibility.This imitating cell outer-layer membrane structure it is material modified, will, organizational project material implanted in blood purification, the field such as medicament slow release and biology sensor has broad application prospects.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to one kind contains ammonia
The phosphoryl choline polymer of base and the method for glutaraldehyde bionic coating density.
Background technology
Shitosan has the advantages that degradability, antibiotic property, nontoxic, non-stimulated, pH responses (Carbohydrate
Polymers2010,79:724-730), it has been widely used in the fields such as biomedicine.Increasing research shows：Shell
Glycan and its derivant material can be used for blood purification.Amino in chitosan molecule contributes to various toxin in blood
Absorption, can be used for blood Absorbent (SCI 2002,23:75-77；Journal of
Microencapsulation 1993,10:475-486).Chitosan film has dialysance high, selectivity and intensity, can be with
As haemodialysis material (Journal of Applied Polymer Science 1992,46:255-261；263-269).
Although Chitosan-phospholipid complex has many advantages as blood purification material, protein absorption is there is also, blood is small
Plate sticks, and ultimately results in blood coagulation, the problems such as form thrombus, so the blood compatibility for improving Chitosan-phospholipid complex material is compeled
In the eyebrows and eyelashes (Applied Surface Science 2005,241:485-492；Biomaterials 2002,23:2561-
2568；Biomaterials 2003,24:3213-3220).
Phosphorylcholine (phosphorylcholine, PC) is the terminal hydrophyllic group for constituting cell membrane elementary cell lecithin, is
Outer layer functional group in extracellular tunic, simultaneous with positive and negative xenogenesis electric charge, ability and hydrophily with stronger combination water
Can, the surface of this structure and composition interacts with physiological environment and will not only adsorb and depositing proteins, will not also trigger
Platelet activation, cause the adverse reactions such as blood coagulation, with good biocompatibility.Research in recent years shows, using phosphinylidyne
Choline group and its polymer build in material surface has imitating cell outer-layer membrane structure, can significantly improve the blood phase of material
Capacitive.
In recent years, using approach (the Carbohydrate Polymers 2007,70 of grafting Phosphorylcholine small molecule:82-
88；Biomacromolecules 2007,8:3169-3176；Biomacromolecules 2006,7:3151-3156；
Journal of Applied Polymer Science 2003,88:489-493；Polymer International
2003,52:81-85；Journal of biomaterials science,Polymer edition 2002,13:501-
510；Colloids and Surfaces B:Biointerfaces2009,71:268-274) modification of chitosan so that shell gathers
The blood compatibility of sugar is significantly improved.But, these modes are not often high in the density of the Phosphorylcholine group of material surface, limit
It has been made in the application in the modified field of bio-medical material and the further raising of blood compatibility.
Therefore, by the methacrylic acid containing Phosphorylcholine group-methylacryoyloxyethyl Phosphorylcholine binary copolymerization
Thing (PMA) polyanion, layer upon layer electrostatic self assembly is carried out with shitosan (polycation), is obtained with imitating cell outer-layer film knot
Coating surface (the Colloids and Surfaces B of structure:Biointerfaces 2011,85:48-55).Protein is adsorbed
With platelet adhesion reaction test result indicate that：The blood compatibility on modified surface is obviously improved.In view of this modified side
A variety of advantages of method, will provide technical support to lift the blood compatibility of bio-medical material.However, with physical absorption side
Formula combines the polymer with simulated cellulosa membrane structure coating in transplanting device surface, occurs unavoidably in complex environment in vivo molten
Solve, come off.Therefore, Lewis and Xu build equality (Biomaterials 2001,22:99-111；Biomaterials 2004,
25:3099-3108；European Polymer Journal 2004,40:291-298) respectively to containing trimethoxy silicon substrate
The polymer coating of group and Phosphorylcholine group is studied.Result shows, trimethoxy on polymer molecular chain in coating
Silicon group is met water and can hydrolyze, be crosslinked, and also covalent bond can be formed with the active group of substrate surface, so that Phosphorylcholine class
The performance of polymer coating is significantly improved.As can be seen here, between polymer crosslinking and its with substrate surface functional group
Reaction, is to improve Phosphorylcholine to birds of the same feather flock together the key factor of compound coating performance.
Crosslinkable groups are incorporated into phosphoryl choline polymer can form metastable imitating cell outer-layer membrane structure coating,
But this phosphoryl choline polymer synthesis for building stable coatings is complicated, undesirable using relatively difficult, stability.In addition, receiving
In polymer the limitation of Phosphorylcholine content and coating dry, migration in the Phosphorylcholine group orientation of surface during storage, cause
Make coating surface Phosphorylcholine groups density relatively low, be difficult effectively analog cell outer layer membrane structure, blood compatibility need
Improve.Therefore, building Stability Analysis of Structures, Phosphorylcholine groups density imitating cell outer-layer membrane structure coating high has important research
Meaning and application prospect.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned the deficiencies in the prior art, there is provided a kind of containing amino
Phosphoryl choline polymer and the method for glutaraldehyde bionic coating density.Stabilization of the invention, Phosphorylcholine groups density are high to imitate
The preparation method of cell outer-layer membrane structure coating is simple, mild condition, to obtain the imitating cell outer-layer membrane structure of excellent performance
Coating surface provides a kind of new approach.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of phosphoryl choline polymer containing amino and the method for glutaraldehyde bionic coating density, it is characterised in that bag
Include following steps：
Step one, the vinyl monomer containing amphion Phosphorylcholine group and the vinyl monomer containing amino are existed
Solution free radical polymerization is carried out under initiator effect, synthesizes the phosphoryl choline polymer containing amino；
Step 2, the phosphoryl choline polymer containing amino is dissolved in polar solvent with glutaraldehyde it is well mixed, coats
Modified material surface is being needed, is being dried；Amino wherein in the phosphoryl choline polymer containing amino and aldehyde radical in glutaraldehyde
Mol ratio be about (100: 5)~(100: 20)；
Step 3, will be dried in step 2 after material to be modified be placed in the ethene containing amphion Phosphorylcholine group
In the solution of base monomer, 5h~12h is reacted under the conditions of 20 DEG C~40 DEG C；
Step 4, the film that will be processed in step 3 are placed in distilled water, and 2h~12h is processed under the conditions of 80 DEG C~95 DEG C,
Washed with solvent again, you can obtain surface Phosphorylcholine density imitating cell outer-layer membrane structure coating high.
In step one, the vinyl monomer containing amphion Phosphorylcholine group is 2- methylacryoyloxyethyls
Phosphorylcholine monomer, the vinyl monomer containing amino is 2- aminoethyl methacrylate hydrochloric acid salt monomers, described to draw
Hair agent is potassium peroxydisulfate.
In step one, the vinyl monomer containing amphion Phosphorylcholine group and the vinyl list containing amino
Body mol ratio is (90:10)~(60:40).
In step one, the vinyl monomer containing amphion Phosphorylcholine group and the vinyl list containing amino
Body and initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, the then freeze-drying at -50 DEG C,
Obtain the phosphoryl choline polymer containing amino.
In step 2, the polar solvent is methyl alcohol or ethanol.
In step 2, in the phosphoryl choline polymer containing amino and glutaraldehyde mixed solution, the phosphinylidyne courage containing amino
The concentration of alkali polymer is 0.5~5mg/mL, and coating volume is 10 microlitres/cm2/ face.
In step 3, the solution of the vinyl monomer containing amphion Phosphorylcholine group, concentration be 5~
20mg/mL, solvent is methyl alcohol.
In step 4, the solvent washing refers to successively with methyl alcohol, distillation water washing.
It is described to need modified material for chitosan film in step 2.
The present invention compared with prior art, with advantages below：
The present invention passes through letter by the vinyl monomer containing amphion Phosphorylcholine group, containing amido vinyl monomer
Single solution free radical polymerization, synthesizes the phosphoryl choline polymer containing amino, and itself and glutaraldehyde is dissolved in into polar solvent and mix
Close uniform, be coated in chitosan film surface, dry, be then grafted the vinyl monomer of amphion Phosphorylcholine group.Containing ammonia
The phosphoryl choline polymer of base is using certainly by the vinyl monomer containing Phosphorylcholine and the vinyl monomer containing amino
The binary randomcopolymer synthesized by base polymerization, the bipolymer is well mixed with glutaraldehyde, is coated in chitosan film table
Face, dry, be then grafted the vinyl monomer of amphion Phosphorylcholine group.By Michael's addition by amphion phosphinylidyne
The vinyl monomer-grafted of choline group to coating surface, then by amino and shitosan in temperature control phosphoryl choline polymer
Film surface amino groups are reacted with glutaraldehyde, grappling base material while being crosslinked coat inside so that coating layer thickness reduction is significantly improved
The density of coating surface Phosphorylcholine, you can obtain surface Phosphorylcholine density imitating cell outer-layer membrane structure coating high.
The preparation method of stabilization of the invention, Phosphorylcholine groups density imitating cell outer-layer membrane structure coating high is simple,
Mild condition, a kind of new approach is provided to obtain the coating surface of imitating cell outer-layer membrane structure of excellent performance.The present invention
Stabilization, Phosphorylcholine groups density imitating cell outer-layer membrane structure coating high will be material implanted in blood purification, tissue
The fields such as engineering, medicament slow release and biology sensor have broad application prospects.
Brief description of the drawings
Fig. 1 is the dynamic contact angle comparison diagram of chitosan film (CS) and Chitosan film (CS-PMH20GA-MPC).
Fig. 2 is the fine energy spectrum diagram of surface-element of chitosan film (CS) and Chitosan film (CS-PMH20GA-MPC).
Fig. 3 is the AFM figures of chitosan film (CS) and Chitosan film (CS-PMH20GA-MPC).
Fig. 4 is the fluorescin adsorbance of chitosan film (CS) and Chitosan film (CS-PMH20GA-MPC).
Specific embodiment
A kind of preparation method of surface Phosphorylcholine density of present invention imitating cell outer-layer membrane structure coating high is：General mole
Than being about 90:10~60:40 vinyl monomers containing amphion Phosphorylcholine group and the vinyl monomer containing amino
It is polymerized, is synthesized the phosphoryl choline polymer containing amino, and it is dissolved in methanol solvate with glutaraldehyde be well mixed, painting
Overlay on chitosan film surface, be subsequently placed in the vinyl monomer containing amphion Phosphorylcholine group, 20 DEG C~
5h~12h is reacted under the conditions of 40 DEG C.Afterwards, 2h~12h is heated through distilled water under the conditions of 80 DEG C~95 DEG C, successively with a large amount of
Methyl alcohol, distillation water washing, you can obtain surface Phosphorylcholine density imitating cell outer-layer membrane structure coating high.
With reference to the accompanying drawings and examples, technical scheme is described in further detail.
Embodiment 1
1) 16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol 2- aminoethyl methacrylate salt are weighed
Hydrochlorate, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, so
The freeze-drying at -50 DEG C afterwards, obtains the phosphoryl choline polymer PMH20 (ammonia in 20 representation polymer building-up processes containing amino
The vinyl monomer molar ratio of base is for 20%).
With 400MHz NMRs with D2O is the proton magnetic of solvent test polymer.Appearance is had no at 5~7ppm,
Show there is no residual monomer in gained copolymer, and successfully synthesize the polymer, with 3.28ppm at as-N+(CH3)3Feature
Peak, for the peak of methylene and pendant methyl on main chain calculates polymer composition at 0.9~2.2ppm, it is known that the polymer constitute with
Rate of charge is basically identical.
2) phosphoryl choline polymer containing amino and glutaraldehyde are dissolved in first for 100: 10 by amino and aldehyde radical mol ratio
After being well mixed in alcoholic solvent, make the concentration of the phosphoryl choline polymer containing amino for 1.0mg/mL, 10 microlitres of volume of coating/
cm2/ face is dried on chitosan material (CS) surface, then through in distilled water 90 degree treatment 6h, afterwards successively with substantial amounts of methyl alcohol,
Distillation water washing, you can obtain comparative sample (CS-PMH20/GA), be then soaked in 25mL, the 2- metering systems of 10mg/mL
In the methanol solution of acyloxyethyl Phosphorylcholine, 25 DEG C react 10h, after through in distilled water 90 degree process 6h, afterwards successively
With substantial amounts of methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating (CS-PMH20/GA-
MPC)。
3) phosphoryl choline polymer that the present embodiment is contained amino is 100 by amino and aldehyde radical mol ratio with glutaraldehyde:
After 10 are dissolved in and being well mixed in methanol solvate, make the concentration of the phosphoryl choline polymer containing amino for 1.0mg/mL, coated body
10 microlitres/cm of product2/ face is dried on chitosan material surface, is then soaked in 25mL, the 2- methacryls of 10mg/mL
In the methanol solution of oxygen ethylphosphocholine, 25 DEG C react 10h, after through in distilled water 90 degree process 6h, use successively afterwards
Substantial amounts of methyl alcohol, distillation water washing, you can obtain stablizing the coating surface (CS-PMH20GA-MPC) of imitating cell outer-layer membrane structure.
As shown in figure 1, chitosan material and the chitosan material that through control coatings processes of the present embodiment through coating treatment
Compare, the surface advancing angle through the shitosan of coating treatment is relatively low, because the phosphoryl choline polymer containing amino and penta
It is further that the remaining amino of dialdehyde coating surface is grafted 2- methylacryoyloxyethyl Phosphorylcholine monomers by schiff base reaction
Improve the density of coating surface Phosphorylcholine group so that coating surface hydrophily is higher, and advancing angle is relatively low.
The surface-element content of the chitosan film of table 1. (CS) and Chitosan film (CS-PMH20GA-MPC).
Table 1
As shown in Figure 2 and Table 1, the shitosan that the present embodiment is processed through the chitosan material of coating treatment and through control coatings
Material is compared, N and P characteristic absorption peaks are larger on the chitosan film surface Phosphorylcholine group of modified treatment, surface phosphinylidyne courage
Base groups density is higher.
As shown in figure 3, chitosan material and the chitosan material that through control coatings processes of the present embodiment through coating treatment
Compare, the surface topography through the shitosan of coating treatment is dramatically different.
As shown in figure 4, chitosan material and the chitosan material that through control coatings processes of the present embodiment through coating treatment
Compare, the shitosan fluorescin adsorbance through processing has obvious reduction, blood compatibility is significantly improved.
Embodiment 2
Weigh 17mmol 2- methylacryoyloxyethyls Phosphorylcholines and 3mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 5 molten by amino and aldehyde radical mol ratio with glutaraldehyde
After being well mixed in alcohol solvent, make the concentration of the phosphoryl choline polymer containing amino for 0.5mg/mL, coat volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 20mL, the 2- methylacryoyloxyethyls of 5mg/mL
In the methanol solution of Phosphorylcholine, 12h are reacted at 20 DEG C, after process 12h through 80 degree in distilled water, afterwards successively with substantial amounts of
Methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 3
Weigh 12mmol 2- methylacryoyloxyethyls Phosphorylcholines and 8mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 15 by amino and aldehyde radical mol ratio with glutaraldehyde
It is dissolved in after being well mixed in methanol solvate, makes the concentration of the phosphoryl choline polymer containing amino for 1.5mg/mL, coats volume
10 microlitres/cm2/ face is dried on chitosan material surface, is then soaked in 25mL, the 2- methacryloxypropyls of 15mg/mL
In the methanol solution of ethylphosphocholine, 30 DEG C react 8h, after through in distilled water 85 degree treatment 10h, afterwards successively with greatly
The methyl alcohol of amount, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 4
Weigh 15mmol 2- methylacryoyloxyethyls Phosphorylcholines and 5mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 20 by amino and aldehyde radical mol ratio with glutaraldehyde
It is dissolved in after being well mixed in alcohol solvent, makes the concentration of the phosphoryl choline polymer containing amino for 2mg/mL, coats volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 30mL, the 2- methacryloxypropyl second of 20mg/mL
In the methanol solution of base Phosphorylcholine, 6h are reacted at 35 DEG C, after process 2h through 95 degree in distilled water, afterwards successively with substantial amounts of
Methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 5
Weigh 14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 8 molten by amino and aldehyde radical mol ratio with glutaraldehyde
After being well mixed in methanol solvate, make the concentration of the phosphoryl choline polymer containing amino for 3mg/mL, coating volume 10 is micro-
Liter/cm2/ face is dried on chitosan material surface, is then soaked in 22mL, the 2- methylacryoyloxyethyl phosphorus of 7mg/mL
In the methanol solution of phatidylcholine, 40 DEG C react 5h, after through in distilled water 83 degree process 11h, use substantial amounts of first successively afterwards
Alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 6
Weigh 13mmol 2- methylacryoyloxyethyls Phosphorylcholines and 7mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 12 by amino and aldehyde radical mol ratio with glutaraldehyde
It is dissolved in after being well mixed in alcohol solvent, makes the concentration of the phosphoryl choline polymer containing amino for 4mg/mL, coats volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 27mL, the 2- methacryloxypropyl second of 17mg/mL
In the methanol solution of base Phosphorylcholine, 22 DEG C react 11h, after through in distilled water 87 degree treatment 8h, afterwards successively with largely
Methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 7
Weigh 16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 17 by amino and aldehyde radical mol ratio with glutaraldehyde
It is dissolved in after being well mixed in methanol solvate, makes the concentration of the phosphoryl choline polymer containing amino for 5mg/mL, coats volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 23mL, the 2- methacryloxypropyl second of 14mg/mL
In the methanol solution of base Phosphorylcholine, 7h are reacted at 32 DEG C, after process 3h through 92 degree in distilled water, afterwards successively with substantial amounts of
Methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 8
Weigh 18mmol 2- methylacryoyloxyethyls Phosphorylcholines and 2mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, with 0.1mmol potassium peroxydisulfates as initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then
The freeze-drying at -50 DEG C, obtains the phosphoryl choline polymer containing amino.
The phosphoryl choline polymer that the present embodiment is contained into amino is 100: 18 by amino and aldehyde radical mol ratio with glutaraldehyde
It is dissolved in after being well mixed in methanol solvate, makes the concentration of the phosphoryl choline polymer containing amino for 5mg/mL, coats volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 23mL, the 2- methacryloxypropyl second of 14mg/mL
In the methanol solution of base Phosphorylcholine, 7h are reacted at 32 DEG C, after process 3h through 92 degree in distilled water, afterwards successively with substantial amounts of
Methyl alcohol, distillation water washing, you can obtain highdensity imitating cell outer-layer membrane structure coating surface.
The above, is only presently preferred embodiments of the present invention, and any limitation is not done to the present invention, 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 (9)
1. a kind of method of phosphoryl choline polymer containing amino and glutaraldehyde bionic coating density, it is characterised in that including
Following steps：
Step one, the vinyl monomer containing amphion Phosphorylcholine group and the vinyl monomer containing amino are being triggered
Solution free radical polymerization is carried out under agent effect, synthesizes the phosphoryl choline polymer containing amino；
Step 2, the phosphoryl choline polymer containing amino is dissolved in polar solvent with glutaraldehyde it is well mixed, being coated in needs
The material surface to be modified, dries；Amino wherein in the phosphoryl choline polymer containing amino rubs with aldehyde radical in glutaraldehyde
You are than being (100: 5)~(100: 20)；
Step 3, will be dried in step 2 after material to be modified be placed in the vinyl list containing amphion Phosphorylcholine group
In the solution of body, 5h~12h is reacted under the conditions of 20 DEG C~40 DEG C；
Step 4, the film that will be processed in step 3 are placed in distilled water, 2h~12h are processed under the conditions of 80 DEG C~95 DEG C, then use
Solvent is washed, you can obtain surface Phosphorylcholine density imitating cell outer-layer membrane structure coating high.
2. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step one, the vinyl monomer containing amphion Phosphorylcholine group is 2- methacryls
Oxygen ethylphosphocholine monomer, the vinyl monomer containing amino is 2- aminoethyl methacrylate hydrochloric acid salt monomers,
The initiator is potassium peroxydisulfate.
3. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step one, the vinyl monomer containing amphion Phosphorylcholine group and the second containing amino
Alkenyl monomer mol ratio is (90:10)~(60:40).
4. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step one, the vinyl monomer containing amphion Phosphorylcholine group and the second containing amino
Alkenyl monomer and initiator, under nitrogen protection, 70 DEG C of polymerisation 24h, reaction is dialysed after terminating, then cold at -50 DEG C
It is lyophilized dry, obtain the phosphoryl choline polymer containing amino.
5. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step 2, the polar solvent is methyl alcohol or ethanol.
6. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
In method, it is characterised in that in step 2, the phosphoryl choline polymer containing amino and glutaraldehyde mixed solution, contain amino
The concentration of phosphoryl choline polymer is 0.5~5mg/mL, and coating volume is 10 microlitres/cm2/ face.
7. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step 3, the solution of the vinyl monomer containing amphion Phosphorylcholine group, concentration is 5
~20mg/mL, solvent is methyl alcohol.
8. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step 4, the solvent washing refers to successively with methyl alcohol, distillation water washing.
9. the side of a kind of phosphoryl choline polymer containing amino according to claim 1 and glutaraldehyde bionic coating density
Method, it is characterised in that in step 2, it is described to need modified material for chitosan film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113692429A (en) * | 2019-02-15 | 2021-11-23 | 敏锐聚合物有限公司 | Biocompatible polymer coatings containing therapeutic agents |
| CN113877006A (en) * | 2021-09-24 | 2022-01-04 | 宁波健世科技股份有限公司 | Modified polymer membrane material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531740A (en) * | 2009-01-12 | 2009-09-16 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN102888013A (en) * | 2011-07-20 | 2013-01-23 | 西北大学 | Method for constructing simulated outer cell membrane structure coating on material surface by RAFT (reversible addition fragmentation chain transfer) polymerization technology |
| CN105237778A (en) * | 2015-11-16 | 2016-01-13 | 西安科技大学 | Method for improving chitosan blood compatibility under room temperature |
| CN105670022A (en) * | 2016-02-25 | 2016-06-15 | 西安科技大学 | Preparation method of phosphorylcholine bionic coating |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531740A (en) * | 2009-01-12 | 2009-09-16 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN102888013A (en) * | 2011-07-20 | 2013-01-23 | 西北大学 | Method for constructing simulated outer cell membrane structure coating on material surface by RAFT (reversible addition fragmentation chain transfer) polymerization technology |
| CN105237778A (en) * | 2015-11-16 | 2016-01-13 | 西安科技大学 | Method for improving chitosan blood compatibility under room temperature |
| CN105670022A (en) * | 2016-02-25 | 2016-06-15 | 西安科技大学 | Preparation method of phosphorylcholine bionic coating |
Non-Patent Citations (1)
| Title |
|---|
| 梁飞，余丽丽，李立，范涛，王小库，陈科洁: "可降解聚碳酸酯基聚氨酯的仿生改性及其性能研究", 《现代化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113692429A (en) * | 2019-02-15 | 2021-11-23 | 敏锐聚合物有限公司 | Biocompatible polymer coatings containing therapeutic agents |
| CN113692429B (en) * | 2019-02-15 | 2023-08-04 | 敏锐聚合物有限公司 | Biocompatible polymer coating containing therapeutic agents |
| CN113877006A (en) * | 2021-09-24 | 2022-01-04 | 宁波健世科技股份有限公司 | Modified polymer membrane material and preparation method thereof |
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