CN106905554B - A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating - Google Patents
A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating Download PDFInfo
- Publication number
- CN106905554B CN106905554B CN201710118250.9A CN201710118250A CN106905554B CN 106905554 B CN106905554 B CN 106905554B CN 201710118250 A CN201710118250 A CN 201710118250A CN 106905554 B CN106905554 B CN 106905554B
- Authority
- CN
- China
- Prior art keywords
- phosphoryl choline
- glutaraldehyde
- containing amino
- amino
- choline polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2443/02—Homopolymers or copolymers of monomers containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The present invention is a kind of method of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating.Vinyl monomer containing amphoteric ion Phosphorylcholine group, the vinyl monomer containing amino are passed through simple solution free radical polymerization by the present invention, synthesize the phosphoryl choline polymer containing amino, and it is dissolved in polar solvent with glutaraldehyde and is uniformly mixed, coated in the modified material surface of needs through handling, then it is grafted the vinyl monomer of amphoteric ion Phosphorylcholine group, can be obtained the high imitating cell outer-layer membrane structure coating of surface Phosphorylcholine density.This preparation method is simple, mild condition, and obtaining the excellent coating surface of blood compatibility to improve coating surface Phosphorylcholine density provides a kind of new approach.The modified material of this imitating cell outer-layer membrane structure, will be in blood purification, and material implanted, organizational project, the fields such as medicament slow release and biosensor have 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 method of the phosphoryl choline polymer and the density of glutaraldehyde bionic coating of base.
Background technique
Chitosan has many advantages, such as degradability, antibiotic property, nontoxic, non-stimulated, pH responsiveness (Carbohydrate
Polymers2010,79:724-730), it has been widely used in the fields such as biomedicine.More and more researches show that: shell
Glycan and its derivant material can be used for blood purification.Amino in chitosan molecule facilitates to toxin a variety of in blood
Absorption, can be used for blood Absorbent (Chemical Journal of Chinese Universities 2002,23:75-77；Journal of
Microencapsulation 1993,10:475-486).Chitosan film has high dialysance, selectivity and intensity, can be with
As haemodialysis material (Journal of Applied Polymer Science 1992,46:255-261；263-269).
Although chitosan and its derivative has many advantages as blood purification material, there is also protein absorption, and blood is small
The problems such as plate sticks, and eventually leads to blood coagulation, forms thrombus, so the blood compatibility for improving chitosan and its derivative 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 forming cell membrane basic unit lecithin, is
Outer layer functional group in extracellular tunic, simultaneous with positive and negative xenogenesis charge, ability and hydrophily with stronger combination water
Can, the surface of this structure and composition will not only be adsorbed with physiological environment interaction and depositing proteins, will not cause
Platelet activation leads to the adverse reactions such as blood coagulation, has good biocompatibility.In recent years studies have shown that using phosphinylidyne
Choline group and its polymer construct on the surface of the material has imitating cell outer-layer membrane structure, can significantly improve the blood phase of material
Capacitive.
In recent years, using approach (the Carbohydrate Polymers 2007,70:82- of grafting Phosphorylcholine small molecule
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 is poly-
The blood compatibility of sugar significantly improves.But the density of the Phosphorylcholine group of these modes often on the surface of the material is not high, limit
It has been made in the modified application in field of bio-medical material and further increasing for blood compatibility.
For this purpose, by the methacrylic acid containing Phosphorylcholine group-methylacryoyloxyethyl Phosphorylcholine binary copolymerization
Object (PMA) polyanion carries out layer upon layer electrostatic self assembly with chitosan (polycation), obtains with imitating cell outer-layer film knot
The coating surface (Colloids and Surfaces B:Biointerfaces 2011,85:48-55) of structure.Protein absorption
With platelet adhesion reaction the results showed that the blood compatibility of modified rear surface is obviously improved.In view of this modification side
The all the advantages of method will provide technical support to promote the blood compatibility of bio-medical material.However, with physical absorption side
Formula is incorporated in the polymer with simulated cellulosa membrane structure coating of transplanting device surface, inevitably occurs in complex environment in vivo molten
It solves, fall off.For this purpose, Lewis and Xu Jian equality (Biomaterials 2001,22:99-111；Biomaterials 2004,
25:3099-3108；European Polymer Journal 2004,40:291-298) respectively to contain trimethoxy silicon substrate
The polymer coating of group and Phosphorylcholine group is studied.The result shows that trimethoxy on polymer molecular chain in coating
Silicon group, which meets water, can occur hydrolysis, crosslinking, covalent bond can also be formed with the active group of substrate surface, to make Phosphorylcholine class
The performance of polymer coating is significantly improved.It can be seen that between polymer crosslinking and its with substrate surface functional group
Reaction is the key factor for improving Phosphorylcholine quasi polymer coating performance.
Crosslinkable groups, which are introduced into phosphoryl choline polymer, can form metastable imitating cell outer-layer membrane structure coating,
But the phosphoryl choline polymer of this building stable coatings synthesizes complexity, using relatively difficult, stability is undesirable.In addition, by
The limitation of Phosphorylcholine content and coating be dry in polymer, migration in the Phosphorylcholine group orientation of surface during storage, causes
Keep coating surface Phosphorylcholine groups density lower, be not easy effective simulation cell outer-layer membrane structure, blood compatibility need
It improves.Therefore, constructing the high imitating cell outer-layer membrane structure coating of stable structure, Phosphorylcholine groups density has important research
Meaning and application prospect.
Summary of the invention
It is a kind of containing amino technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, providing
The method of phosphoryl choline polymer and the density of glutaraldehyde bionic coating.High imitative of stabilization of the invention, Phosphorylcholine groups density
The preparation method of cell outer-layer membrane structure coating is simple, mild condition, to obtain the imitating cell outer-layer membrane structure haveing 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 that:
A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating, which is characterized in that packet
Include following steps:
Step 1: the vinyl monomer containing amphoteric ion Phosphorylcholine group and the vinyl monomer containing amino are existed
Initiator effect is lower to carry out solution free radical polymerization, synthesizes the phosphoryl choline polymer containing amino；
It is uniformly mixed, coats Step 2: the phosphoryl choline polymer containing amino is dissolved in polar solvent with glutaraldehyde
Modified material surface is being needed, is being dried；Wherein aldehyde radical in the amino and glutaraldehyde in the phosphoryl choline polymer containing amino
Molar ratio be about (100: 5)~(100: 20)；
Step 3: the material to be modified after drying in step 2 is placed in the ethylene containing amphoteric ion 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 handled in step 3 is placed in distilled water, 2h~12h is handled under the conditions of 80 DEG C~95 DEG C,
It is washed again with solvent, the high imitating cell outer-layer membrane structure coating of surface Phosphorylcholine density can be obtained.
In step 1, the vinyl monomer containing amphoteric ion Phosphorylcholine group is 2- methylacryoyloxyethyl
Phosphorylcholine monomer, the vinyl monomer containing amino is 2- aminoethyl methacrylate hydrochloric acid salt monomer, described to draw
Hair agent is potassium peroxydisulfate.
In step 1, the vinyl monomer containing amphoteric ion Phosphorylcholine group and the vinyl list containing amino
Body molar ratio is (90:10)~(60:40).
In step 1, the vinyl monomer containing amphoteric ion Phosphorylcholine group and the vinyl list containing amino
Body and initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed after reaction, are then freeze-dried at -50 DEG C,
Obtain amino-containing phosphoryl choline polymer.
In step 2, the polar solvent is methanol or ethyl alcohol.
In step 2, in the phosphoryl choline polymer containing amino and glutaraldehyde mixed solution, the phosphinylidyne gallbladder 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 amphoteric ion Phosphorylcholine group, concentration be 5~
20mg/mL, solvent are methanol.
In step 4, the solvent washing refers to successively with methanol, distillation water washing.
It is described to need modified material for chitosan film in step 2.
Compared with prior art, the present invention having the advantage that
The present invention passes through letter by the vinyl monomer containing amphoteric ion Phosphorylcholine group, containing amido vinyl monomer
Single solution free radical polymerization synthesizes the phosphoryl choline polymer containing amino, and it is dissolved in polar solvent with glutaraldehyde and is mixed
It closes uniformly, coated in chitosan film surface, dries, be then grafted the vinyl monomer of amphoteric ion Phosphorylcholine group.Containing ammonia
The phosphoryl choline polymer of base is used certainly by the vinyl monomer containing Phosphorylcholine and the vinyl monomer containing amino
The binary randomcopolymer synthesized by base polymerization, the bipolymer are uniformly mixed with glutaraldehyde, are coated in chitosan film table
Face is dried, and the vinyl monomer of amphoteric ion Phosphorylcholine group is then grafted.By Michael's addition by amphoteric ion phosphinylidyne
The vinyl monomer-grafted of choline group controls amino and chitosan in phosphoryl choline polymer to coating surface, then by temperature
Film surface amino is reacted with glutaraldehyde, and substrate is anchored while being crosslinked coat inside, so that coating layer thickness reduction significantly improves
The density of coating surface Phosphorylcholine can be obtained the high imitating cell outer-layer membrane structure coating of surface Phosphorylcholine density.
The preparation method of the high imitating cell outer-layer membrane structure coating of stabilization of the invention, Phosphorylcholine groups density is simple,
Mild condition provides a kind of new approach to obtain the coating surface for the imitating cell outer-layer membrane structure haveing excellent performance.The present invention
Stabilization, the high imitating cell outer-layer membrane structure coating of Phosphorylcholine groups density will be in blood purification, material implanted, tissue
The fields such as engineering, medicament slow release and biosensor have broad application prospects.
Detailed description of the invention
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 chitosan film (CS) and the AFM figure of 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 imitating cell outer-layer membrane structure coating that Phosphorylcholine density in surface is high of the present invention the preparation method comprises the following steps: will mole
Than be about 90:10~60:40 vinyl monomer for containing amphoteric ion Phosphorylcholine group with containing the vinyl monomer of amino
It is polymerize, synthesizes the phosphoryl choline polymer containing amino, and it is dissolved in methanol solvate with glutaraldehyde and is uniformly mixed, is applied
Overlay on chitosan film surface, be subsequently placed in the vinyl monomer containing amphoteric ion Phosphorylcholine group, 20 DEG C~
5h~12h is reacted under the conditions of 40 DEG C.Later, heat 2h~12h through distilled water under the conditions of 80 DEG C~95 DEG C, successively with a large amount of
Methanol, distillation water washing, the high imitating cell outer-layer membrane structure coating of surface Phosphorylcholine density can be obtained.
With reference to the accompanying drawings and examples, technical solution of the present invention is described in further detail.
Embodiment 1
1) 16mmol 2- methylacryoyloxyethyl Phosphorylcholine and 4mmol 2- aminoethyl methacrylate salt are weighed
Hydrochlorate, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, so after reaction
It is freeze-dried at -50 DEG C afterwards, obtains amino-containing phosphoryl choline polymer PMH20 (ammonia in 20 representation polymer synthesis processes
20%) the vinyl monomer molar ratio of base is.
With 400MHz Nuclear Magnetic Resonance 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, at 3.28ppm for-N+(CH3)3Feature
Peak calculates polymer composition for methylene on main chain and the peak of pendant methyl at 0.9~2.2ppm, it is known that polymer composition with
Feed ratio is almost the same.
2) phosphoryl choline polymer containing amino and glutaraldehyde are dissolved in first by amino and aldehyde radical molar ratio for 100: 10
In alcoholic solvent after mixing, make the concentration 1.0mg/mL of the phosphoryl choline polymer containing amino, 10 microlitres of volume of coating/
cm2/ face is dried on the surface chitosan material (CS), then through 90 degree of processing 6h in distilled water, later successively with a large amount of methanol,
Water washing is distilled, contrast sample (CS-PMH20/GA) can be obtained, be then soaked in 25mL, the 2- metering system of 10mg/mL
In the methanol solution of acyloxyethyl Phosphorylcholine, in 25 DEG C of reaction 10h, after through 90 degree of processing 6h in distilled water, later successively
With a large amount of methanol, distillation water washing, highdensity imitating cell outer-layer membrane structure coating (CS-PMH20/GA- can be obtained
MPC)。
3) the present embodiment is contained into the phosphoryl choline polymer of amino and glutaraldehyde by amino and aldehyde radical molar ratio is 100:
10 are dissolved in methanol solvate the concentration 1.0mg/mL for making the phosphoryl choline polymer containing amino after mixing, coated body
10 microlitres/cm of product2/ face is dried on chitosan material surface, is then soaked in 25mL, the 2- methacryl of 10mg/mL
In the methanol solution of oxygen ethylphosphocholine, in 25 DEG C of reaction 10h, after through 90 degree of processing 6h in distilled water, successively use later
A large amount of methanol, distillation water washing, can be obtained the coating surface (CS-PMH20GA-MPC) of stable imitating cell outer-layer membrane structure.
As shown in Figure 1, chitosan material of the present embodiment through coating treatment and the chitosan material handled through control coatings
It compares, the surface advancing angle of the chitosan through coating treatment is lower, this is because the phosphoryl choline polymer containing amino and penta
The remaining amino of dialdehyde coating surface is further by schiff base reaction grafting 2- methylacryoyloxyethyl Phosphorylcholine monomer
The density of coating surface Phosphorylcholine group is improved, so that coating surface hydrophily is higher, advancing angle is lower.
The surface-element content of 1. chitosan film of table (CS) and Chitosan film (CS-PMH20GA-MPC).
Table 1
As shown in Figure 2 and Table 1, chitosan material of the present embodiment through coating treatment and the chitosan handled through control coatings
Material is compared, N and P characteristic absorption peak is larger on the chitosan film surface Phosphorylcholine group of modified processing, surface phosphinylidyne gallbladder
Base groups density is higher.
As shown in figure 3, chitosan material of the present embodiment through coating treatment and the chitosan material handled through control coatings
It compares, the surface topography of the chitosan through coating treatment is dramatically different.
As shown in figure 4, chitosan material of the present embodiment through coating treatment and the chitosan material handled through control coatings
It compares, processed chitosan fluorescin adsorbance has apparent reduction, and blood compatibility significantly improves.
Embodiment 2
Weigh 17mmol 2- methylacryoyloxyethyl Phosphorylcholine and 3mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 5 molten by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
In alcohol solvent after mixing, make the concentration 0.5mg/mL of the phosphoryl choline polymer containing amino, coat volume 10
Microlitre/cm2/ face is dried on chitosan material surface, is then soaked in 20mL, the 2- methylacryoyloxyethyl of 5mg/mL
In the methanol solution of Phosphorylcholine, in 20 DEG C of reaction 12h, after through 80 degree of processing 12h in distilled water, later successively with a large amount of
Methanol, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 3
Weigh 12mmol 2- methylacryoyloxyethyl Phosphorylcholine and 8mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 15 by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
It is dissolved in methanol solvate the concentration 1.5mg/mL for making the phosphoryl choline polymer containing amino after mixing, coats volume
10 microlitres/cm2/ face is dried on chitosan material surface, is then soaked in 25mL, the 2- methacryloxypropyl of 15mg/mL
In the methanol solution of ethylphosphocholine, in 30 DEG C of reaction 8h, after through 85 degree of processing 10h in distilled water, later successively with big
The methanol of amount, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 4
Weigh 15mmol 2- methylacryoyloxyethyl Phosphorylcholine and 5mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 20 by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
It is dissolved in alcohol solvent the concentration 2mg/mL for making the phosphoryl choline polymer containing amino after mixing, 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, in 35 DEG C of reaction 6h, after through 95 degree of processing 2h in distilled water, later successively with a large amount of
Methanol, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 5
Weigh 14mmol 2- methylacryoyloxyethyl Phosphorylcholine and 6mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 8 molten by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
In methanol solvate after mixing, make the concentration 3mg/mL of the phosphoryl choline polymer containing amino, 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, in 40 DEG C of reaction 5h, after through 83 degree of processing 11h in distilled water, later successively with a large amount of first
Alcohol, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 6
Weigh 13mmol 2- methylacryoyloxyethyl Phosphorylcholine and 7mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 12 by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
It is dissolved in alcohol solvent the concentration 4mg/mL for making the phosphoryl choline polymer containing amino after mixing, 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, in 22 DEG C of reaction 11h, after through 87 degree of processing 8h in distilled water, later successively with a large amount of
Methanol, distillation water washing, highdensity imitating cell outer-layer membrane structure coating surface can be obtained.
Embodiment 7
Weigh 16mmol 2- methylacryoyloxyethyl Phosphorylcholine and 4mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 17 by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
It is dissolved in methanol solvate the concentration 5mg/mL for making the phosphoryl choline polymer containing amino after mixing, 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, in 32 DEG C of reaction 7h, after through 92 degree of processing 3h in distilled water, later successively with a large amount of
Methanol, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
Embodiment 8
Weigh 18mmol 2- methylacryoyloxyethyl Phosphorylcholine and 2mmol 2- aminoethyl methacrylate hydrochloric acid
Salt, using 0.1mmol potassium peroxydisulfate as initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed, then after reaction
It is freeze-dried at -50 DEG C, obtains amino-containing phosphoryl choline polymer.
It by amino and aldehyde radical molar ratio is 100: 18 by phosphoryl choline polymer and glutaraldehyde that the present embodiment contains amino
It is dissolved in methanol solvate the concentration 5mg/mL for making the phosphoryl choline polymer containing amino after mixing, 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, in 32 DEG C of reaction 7h, after through 92 degree of processing 3h in distilled water, later successively with a large amount of
Methanol, distillation water washing, can be obtained highdensity imitating cell outer-layer membrane structure coating surface.
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, all according to invention skill
Art any simple modification substantially to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention
In the protection scope of scheme.
Claims (6)
1. a kind of method of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating, which is characterized in that including
Following steps:
Step 1: the vinyl monomer containing amphoteric ion Phosphorylcholine group and the vinyl monomer containing amino are being caused
Agent effect is lower to carry out solution free radical polymerization, synthesizes the phosphoryl choline polymer containing amino；
The vinyl monomer containing amphoteric ion Phosphorylcholine group is 2- methylacryoyloxyethyl Phosphorylcholine monomer,
The vinyl monomer containing amino is 2- aminoethyl methacrylate hydrochloric acid salt monomer, and the initiator is persulfuric acid
Potassium；
The vinyl monomer containing amphoteric ion Phosphorylcholine group is with the vinyl monomer molar ratio containing amino
(90:10)~(60:40)；
It is uniformly mixed Step 2: the phosphoryl choline polymer containing amino is dissolved in polar solvent with glutaraldehyde, being coated in needs
The material surface to be modified, dries；Wherein aldehyde radical rubs in the amino and glutaraldehyde in the phosphoryl choline polymer containing amino
You are than being (100: 5)~(100: 20)；Needing modified material is chitosan film；
Step 3: the material to be modified after drying in step 2 is placed in the vinyl list containing amphoteric ion 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 handled in step 3 is placed in distilled water, 2h~12h is handled under the conditions of 80 DEG C~95 DEG C, then use
Solvent washing, can be obtained the high imitating cell outer-layer membrane structure coating of surface Phosphorylcholine density.
2. the side of a kind of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating according to claim 1
Method, which is characterized in that in step 1, the vinyl monomer containing amphoteric ion Phosphorylcholine group and contain the second of amino
Alkenyl monomer and initiator, under nitrogen protection, 70 DEG C of polymerization reactions for 24 hours, are dialysed after reaction, then cold at -50 DEG C
It is lyophilized dry, obtains amino-containing phosphoryl choline polymer.
3. the side of a kind of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating according to claim 1
Method, which is characterized in that in step 2, the polar solvent is methanol or ethyl alcohol.
4. the side of a kind of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating according to claim 1
Method, which is characterized in that in step 2, in 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.
5. the side of a kind of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating according to claim 1
Method, which is characterized in that in step 3, the solution of the vinyl monomer containing amphoteric ion Phosphorylcholine group, concentration 5
~20mg/mL, solvent are methanol.
6. the side of a kind of phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating according to claim 1
Method, which is characterized in that in step 4, the solvent washing refers to successively with methanol, distillation water washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710118250.9A CN106905554B (en) | 2017-03-01 | 2017-03-01 | A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710118250.9A CN106905554B (en) | 2017-03-01 | 2017-03-01 | A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106905554A CN106905554A (en) | 2017-06-30 |
| CN106905554B true CN106905554B (en) | 2019-08-13 |
Family
ID=59185959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710118250.9A Expired - Fee Related CN106905554B (en) | 2017-03-01 | 2017-03-01 | A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905554B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3924432A4 (en) * | 2019-02-15 | 2022-11-09 | Acuity Polymers, Inc. | Biocompatible polymeric 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531740B (en) * | 2009-01-12 | 2012-05-09 | 西北大学 | Method for forming simulated cell outer layer membrane structure on surface of cross-linked chitosan |
| CN102888013B (en) * | 2011-07-20 | 2015-03-25 | 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 |
| CN105237778B (en) * | 2015-11-16 | 2017-10-13 | 西安科技大学 | It is a kind of to improve the method for chitosan blood compatibility at room temperature |
| CN105670022B (en) * | 2016-02-25 | 2018-05-04 | 西安科技大学 | A kind of preparation method of Phosphorylcholine bionic coating |
-
2017
- 2017-03-01 CN CN201710118250.9A patent/CN106905554B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106905554A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108129687B (en) | A kind of surface is the preparation method of the imitating cell outer-layer membrane structure coating of Phosphorylcholine | |
| CN103881126B (en) | A kind of method for improving material blood compatibility | |
| CN105670022B (en) | A kind of preparation method of Phosphorylcholine bionic coating | |
| CN106750450A (en) | Preparation method containing epoxy phosphoryl choline polymer and dopamine crosslinking adhesion bionic coating | |
| CN104744635B (en) | A kind of preparation method of pair of Biomimetic Polymers | |
| CN106380990B (en) | The preparation method of phosphoryl choline polymer containing aldehyde radical and dopamine cross-linked coating | |
| CN106832382B (en) | Coating method of double-bionic dopamine phosphorylcholine substance | |
| CN105237778B (en) | It is a kind of to improve the method for chitosan blood compatibility at room temperature | |
| CN106866883B (en) | A method of the double Biomimetic Polymers of synthesis are reacted with amino based on aldehyde radical | |
| CN107722321B (en) | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and amino | |
| CN106905554B (en) | A method of the phosphoryl choline polymer containing amino and the density of glutaraldehyde bionic coating | |
| CN107674225B (en) | The preparation method of two kinds of phosphoryl choline polymers crosslinking bionic coating containing aldehyde radical and amino | |
| CN105504328B (en) | A kind of room temperature coats the method for improving chitosan film blood compatibility in next step | |
| CN108003369B (en) | A kind of preparation method of the coating surface of imitating cell outer-layer membrane structure | |
| CN104744717A (en) | Method for preparing phosphorylcholine biomimetic coating by photocuring | |
| CN105288731B (en) | A kind of method that epoxy radicals prepares bionic coating with sulfydryl crosslinking | |
| CN108715643A (en) | A kind of preparation method of epoxy and amino phosphoryl choline polymer bionic adhesion coating | |
| CN108715644B (en) | Preparation method of aldehyde group and aminophosphorylcholine polymer bionic adhesion coating | |
| CN108794794B (en) | Method for modifying surface biocompatibility of material and bionic coating prepared by method | |
| CN103275269B (en) | A kind of phosphoryl choline polymer containing aldehyde radical and its preparation method and application | |
| CN108659168B (en) | Double-bionic polymer and preparation method and application thereof | |
| CN104258471A (en) | Graphene oxide modified by imitation cellular outer membrane structure and preparation method of graphene oxide | |
| CN111793399B (en) | Preparation method of two phosphorylcholine coatings containing catechol, amino and carboxyl | |
| CN108517046A (en) | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl | |
| CN111825799A (en) | Preparation method of phosphorylcholine coating containing catechol, amino and carboxyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190710 Address after: 710054 Shaanxi province Xi'an Beilin District Yanta Road No. 58 Applicant after: Xi'an University of Science and Technology Applicant after: Shaanxi coalfield geology Group Co Ltd Address before: 710054 Shaanxi province Xi'an Beilin District Yanta Road No. 58 Applicant before: Xi'an University of Science and Technology |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190813 Termination date: 20200301 |