CN108517046A - The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl - Google Patents
The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl Download PDFInfo
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- 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
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The method of the invention discloses a kind of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl, by the vinyl monomer containing Phosphorylcholine hydrophilic radical and the vinyl monomer containing epoxy by simple solution free radical polymerization, the phosphoryl choline polymer containing epoxy is synthesized.Vinyl monomer containing Phosphorylcholine group and styrene are subjected to free radical polymerization, then sulfydryl is grafted on the phosphoryl choline polymer containing phenyl ring by chloromethylation, sulfydryl nucleophilic substitution again, you can prepare the phosphoryl choline polymer containing sulfydryl.Two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are dissolved in polar solvent, chitosan film surface is coated in, heats in distilled water after dry, you can prepare the crosslinking bionic coating with imitating cell outer-layer membrane structure.This method preparation is simple and convenient to operate, and a kind of new approach is provided to obtain the excellent crosslinking bionic coating of blood compatibility.
Description
Technical field
The invention belongs to material surface science and biological medical polymer material technical field, and in particular to one kind containing ring
The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films of oxygen and sulfydryl.
Background technology
Chitosan has many advantages, such as degradability, antibiotic property, nontoxic, non-stimulated, pH responses (Carbohydrate
Polymers 2010,79:724-730), it has been widely used in the fields such as biomedicine.It is more and more research shows that：
Chitosan and its derivative material can be used for blood purification.Sulfydryl in chitosan molecule contributes to a variety of toxin 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 Science1992,46:255-261；263-269).
Although chitosan and its derivative has many advantages as blood purification material, there is also protein absorption, and blood is small
Plate sticks, the problems such as eventually leading to blood coagulation, form 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 have imitating cell outer-layer membrane structure in material surface 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:Biointerfaces 2009,71:268-274) modification of chitosan so that shell is poly-
The blood compatibility of sugar significantly improves.But these modes are not often high in the density of the Phosphorylcholine group of material surface, limit
It has made it and has been modified the application in field and further increasing for blood compatibility in bio-medical material.
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
Coating surface (the Colloids and Surfaces B of structure:Biointerfaces 2011,85:48-55).Protein adsorbs
With platelet adhesion reaction the experimental 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 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.The result shows that trimethoxy on polymer molecular chain in coating
Silicon group, which meets water, can occur hydrolysis, crosslinking, also covalent bond can be formed with the active group of substrate surface, to make Phosphorylcholine class
The stability of polymer coating is significantly improved.It can be seen that crosslinking between polymer and its with substrate surface functional group
Reaction, be improve Phosphorylcholine Type of Collective object coating stability key factor.
However, polymer crosslinkable groups facile hydrolysis, crosslinking in the synthesis process so that its building-up process condition is excessively
Harshness is difficult to preserve, and causes its application range limited.
Invention content
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide containing epoxy and sulfydryl
Two kinds of phosphoryl choline polymer bionic coating Chitosan films method.With this prepare with imitating cell outer-layer membrane structure,
The excellent crosslinking bionic coating of blood compatibility, the preparation method of the imitating cell outer-layer membrane structure coating are simple and convenient to operate, and are
It obtains the stable coating surface with imitating cell outer-layer membrane structure and provides a kind of new approach.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl, including
Following steps：
Under nitrogen protection, by the vinyl monomer containing epoxy and the vinyl monomer containing Phosphorylcholine in initiator
Under the action of carry out free radical solution polymerization reaction, synthesize the phosphoryl choline polymer containing epoxy；
Under nitrogen protection, the vinyl monomer containing Phosphorylcholine hydrophilic radical, styrene are passed through into solution freedom
Base polymerize, and synthesizes the phosphoryl choline polymer containing phenyl ring, and itself and zinc chloride and chloromethyl ether are carried out chloromethylation, it
Afterwards, nucleophilic substitution is carried out with NaHS, you can prepare the phosphoryl choline polymer containing sulfydryl；
Two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are dissolved with polar solvent, and are coated in chitosan film table
Face, dry be placed in distilled water are heated, that is, prepare the crosslinking bionic coating with imitating cell outer-layer membrane structure.
The vinyl monomer containing Phosphorylcholine hydrophilic radical is with the vinyl monomer molar ratio containing epoxy
(9.5:0.5)~(5:5).
The vinyl monomer containing Phosphorylcholine hydrophilic radical is (9.5 with styrene monomer molar ratio:0.5)~
(5:5)。
The vinyl monomer containing Phosphorylcholine hydrophilic radical is methylacryoyloxyethyl Phosphorylcholine, is contained
The vinyl monomer of epoxy is glycidyl methacrylate.
In phosphoryl choline polymer containing epoxy, solvent is methanol and tetrahydrofuran mixed solvent, and initiator is azo
Bis-isobutyronitrile, reaction temperature are 65~75 DEG C, and the reaction time is 20~26h, and the bag filter for being 7000 with molecular cut off carries out
Dialysis, is freeze-dried at -50 DEG C.
In chloromethyl reaction, the phosphoryl choline polymer chloroform containing phenyl ring and methanol mixed solvent are dissolved, then
Sequentially add zinc chloride, chloromethyl ether is uniformly mixed, 10~20h of reaction at 30~50 DEG C；Phosphorylcholine polymerization containing phenyl ring
The solid-to-liquid ratio of object and chloromethyl ether is 2g:50ml.
It is in sulfydryl nucleophilic substitution, the phosphoryl choline polymer chloroform and methanol mixed solvent of chloromethylation is molten
Then solution is added sulfhydrylation sodium and is uniformly mixed, 10~20h is reacted at 20~30 DEG C；The phosphoryl choline polymer of chloromethylation
Mass ratio with sulfhydrylation sodium is 1:1.
Two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are configured to a concentration of 0.5~10mg/mL solution, and drop Tu exists
The volume on chitosan film surface, drop coating is 10~40 μ L/cm2/ face.
The polar solvent is methanol or ethyl alcohol.
It is that 6~12h is handled in 20~50 DEG C that painting, which is placed on heating temperature in distilled water,.
Preferably, a kind of side of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl
Method is specially：By the methylacryoyloxyethyl Phosphorylcholine monomer containing Phosphorylcholine hydrophilic radical and contain the first of epoxy
Base glycidyl acrylate monomer in molar ratio 6:4 use solution free radical polymerization, Phosphorylcholine of the synthesis containing epoxy poly-
Close object.Meanwhile by methylacryoyloxyethyl Phosphorylcholine monomer and styrene monomer containing Phosphorylcholine hydrophilic radical
In molar ratio 8:2 use solution free radical polymerization, synthesize the phosphoryl choline polymer containing phenyl ring, and by itself and zinc chloride and chlorine
Methyl ether mixes, and stirs evenly and carries out chloromethylation at 40 DEG C, filters later, vacuum drying is detached.Then, by chlorine
The phosphoryl choline polymer and NaHS to methylate is uniformly mixed, and nucleophilic substitution is carried out at 25 DEG C, finally filters, is true
Sky is dry, you can obtains containing sulfydryl phosphoryl choline polymer.Then two kinds of Phosphorylcholines containing epoxy and sulfydryl are polymerize
Object in mass ratio 7:3 are dissolved in methanol solvate and being uniformly mixed, and then by its solution drop Tu on chitosan film surface, drying is placed on
9h is handled in distilled water at 40 DEG C, epoxy in the phosphoryl choline polymer containing epoxy is made to react anchor with chitosan film surface amino groups
Determine base material simultaneously, with the sulfydryl cross-linking reaction in the phosphoryl choline polymer containing sulfydryl, significantly improves coating surface phosphinylidyne courage
The density of base groups, you can obtain the crosslinking bionic coating with imitating cell outer-layer membrane structure.
Compared with the existing technology, the invention has the advantages that：
The present invention passes through the vinyl monomer containing Phosphorylcholine hydrophilic radical and the vinyl monomer containing epoxy
Simple solution free radical polymerization synthesizes the phosphoryl choline polymer containing epoxy.By the vinyl containing Phosphorylcholine group
Monomer carries out free radical polymerization with styrene, is then grafted on sulfydryl by chloromethylation, sulfydryl nucleophilic substitution again and contains
Have on the phosphoryl choline polymer of phenyl ring, you can prepare the phosphoryl choline polymer containing sulfydryl.It will be containing epoxy and sulfydryl
Two kinds of phosphoryl choline polymers are dissolved in polar solvent, are coated in chitosan film surface, and drying is placed in distilled water at heating
Reason makes in the phosphoryl choline polymer containing epoxy epoxy be reacted with chitosan film surface amino groups and is anchored base material simultaneously, with containing
Sulfydryl cross-linking reaction in the phosphoryl choline polymer of sulfydryl, significantly improves the density of coating surface Phosphorylcholine group, you can
Prepare the crosslinking bionic coating with imitating cell outer-layer membrane structure.By the phosphoryl choline polymer containing epoxy and contain sulfydryl
Phosphoryl choline polymer mixed solution is coated in material surface, is prepared with imitating cell outer-layer membrane structure, blood compatibility with this
Excellent crosslinking bionic coating, the preparation method of the imitating cell outer-layer membrane structure coating are simple and convenient to operate, to obtain stabilization
Coating surface with imitating cell outer-layer membrane structure provides a kind of new approach.The imitating cell outer-layer membrane structure coating of the present invention
It will be in blood purification, material implanted, organizational project, before the fields such as medicament slow release and biosensor have wide application
Scape.
Further, two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are dissolved in solvent and are uniformly mixed, then will
Its solution drips Tu on chitosan film surface, keeps epoxy and chitosan film surface amino groups in the phosphoryl choline polymer containing epoxy anti-
Base material should be anchored simultaneously, the sulfydryl cross-linking reaction with the phosphoryl choline polymer containing sulfydryl significantly improves coating surface phosphorus
The density of phatidylcholine group, you can obtain the crosslinking bionic coating with imitating cell outer-layer membrane structure.
Description of the drawings
Fig. 1 is the synthetic route chart of the phosphoryl choline polymer containing sulfydryl；
Fig. 2 is the nuclear magnetic spectrogram of the invention containing sulfydryl phosphoryl choline polymer；
Fig. 3 is the dynamic contact angle of chitosan film of the present invention and Chitosan film；
Fig. 4 is chitosan film of the present invention and Chitosan film surface fine energy spectrum diagram.
Specific implementation mode
The present invention basic principle be：By the vinyl monomer containing Phosphorylcholine hydrophilic radical and contain the second of epoxy
Alkenyl monomer synthesizes the phosphoryl choline polymer containing epoxy by simple solution free radical polymerization.Phosphorylcholine will be contained
The vinyl monomer of group carries out free radical polymerization with styrene, is then incited somebody to action again by chloromethylation, sulfydryl nucleophilic substitution
Sulfydryl is grafted on the phosphoryl choline polymer containing phenyl ring, you can prepares the phosphoryl choline polymer containing sulfydryl.Then will
Two kind phosphoryl choline polymers of the synthesis containing epoxy and sulfydryl are dissolved in polar solvent, are coated in chitosan film surface, dry
It is placed in distilled water and heats, you can prepare the crosslinking bionic coating with imitating cell outer-layer membrane structure.
Present invention will be described in further detail below with reference to the accompanying drawings, described to be explanation of the invention rather than limit
It is fixed.
Embodiment 1
Such as Fig. 1 synthetic route charts, 12mmol 2- methylacryoyloxyethyls Phosphorylcholines and 8mmol metering systems are weighed
Acid glycidyl ester, using 0.1mmol azodiisobutyronitriles as initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent,
Under nitrogen protection, for 24 hours, after reaction, concentration of reaction solution is 6000~8000D with molecular cut off to 70 DEG C of polymerisations
Bag filter dialysis, then be freeze-dried at -50 DEG C, obtain the phosphoryl choline polymer containing epoxy.
10mmol 2- methacryloxyethyls Phosphorylcholines and 10mmol styrene are weighed, with methanol and tetrahydrochysene furan
Muttering, (volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2Protection, 70 DEG C of stirring conditions
Under, by 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator is added
Solution the reaction was continued 20h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D,
It is freeze-dried at -50 DEG C again, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 15h at 40 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 15h are reacted at 25 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
As shown in Fig. 2, the present embodiment contains the nuclear magnetic spectrogram of sulfydryl phosphoryl choline polymer.With 400MHz Nuclear Magnetic Resonance
With D2O is the proton magnetic of solvent test polymer.Appearance is had no at 5~6.6ppm, is shown in gained copolymer without remnants
Monomer, the appearance at 4.8ppm are the residual peaks of aqueous solvent.Appearance difference at 3.2,0.9~2.2 and 6.8~7.8ppm
To contain-N in sulfydryl phosphoryl choline polymer+(CH3)3, methylene and pendant methyl and phenyl ring on main chain.These the result shows that
This method can be prepared containing sulfydryl phosphoryl choline polymer.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy is configured to the methanol solution of 1mg/mL.Then will
For the above-mentioned phosphoryl choline polymer solution drop Tu containing epoxy on chitosan film surface, the volume of drop coating is 30 μ L/cm2/ face.
It is dried in vacuo for 24 hours at 30 DEG C again.Later, it is placed in distilled water the processing 9h at 40 DEG C, makes the phosphoryl choline polymer containing epoxy
Middle epoxy is reacted with chitosan film surface amino groups, by the open loop of epoxy in phosphoryl choline polymer and chitosan film surface amino groups
Reaction anchoring base material, is fixed on chitosan film surface, you can prepare with imitating cell outer-layer membrane structure by Phosphorylcholine group
Bionic coating (control sample).
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 7:3, it is configured to the methanol solution of 1mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain mercapto
For the mixed solution drop Tu of the phosphoryl choline polymer of base on chitosan film surface, the volume of drop coating is 30 μ L/cm2/ face.Again 30
DEG C vacuum drying for 24 hours.Later, it is placed in distilled water the processing 9h at 40 DEG C, makes epoxy in the phosphoryl choline polymer containing epoxy
It while reaction with chitosan film surface sulfydryl, is reacted with sulfydryl in the phosphoryl choline polymer containing sulfydryl, by phosphinylidyne courage
Epoxy and the ring-opening reaction of chitosan film surface amino groups are anchored base material simultaneously in alkali polymer, poly- with the Phosphorylcholine containing sulfydryl
The ring-opening reaction crosslinking for closing sulfydryl in object, is fixed on chitosan film surface by Phosphorylcholine group, significantly improves coating surface
The density of Phosphorylcholine group, you can prepare the crosslinking bionic coating with imitating cell outer-layer membrane structure.
As shown in figure 3, chitosan film of the present embodiment through coating treatment compared with the chitosan film without coating treatment, passes through
The advancing angle and receding angle of the chitosan of coating treatment decrease, this is because the phosphoryl choline polymer of good hydrophilic property is logical
Reacting for sulfydryl in phosphoryl choline polymer of the epoxy with chitosan surface amino groups and containing sulfydryl is crossed, Phosphorylcholine group is consolidated
It is scheduled on the surface of chitosan film, obtains the surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves, advancing angle
It is substantially reduced with receding angle.In addition, the presence of the phosphoryl choline polymer containing sulfydryl increases the hydrophilic of Chitosan film
Property, advancing angle and receding angle all reduce.This phosphoryl choline polymer of explanation containing sulfydryl increases chitosan film surface phosphinylidyne
The density of choline group, so modified advancing angle receding angle decreases.
As shown in figure 4, chitosan film of the present embodiment through coating treatment compared with the chitosan film without coating treatment, passes through
There is N on Phosphorylcholine group on the chitosan film surface of modification+With P characteristic absorption peaks, this illustrates the phosphinylidyne courage of good hydrophilic property
Base groups are fixed on chitosan film surface.Epoxy and chitosan film surface sulfydryl are anti-in phosphoryl choline polymer containing epoxy
While answering, reacted with sulfydryl in the phosphoryl choline polymer containing sulfydryl, it is poly- by epoxy in phosphoryl choline polymer and shell
The ring-opening reaction anchoring of sugared film surface amino simultaneously, is handed over the ring-opening reaction of sulfydryl in the phosphoryl choline polymer containing sulfydryl
Connection, is fixed on chitosan film surface by Phosphorylcholine group, significantly improves the density of coating surface Phosphorylcholine group, can prepare
Surface with imitating cell outer-layer membrane structure so that its hydrophily significantly improves, and N on Phosphorylcholine group occurs+It is inhaled with P features
Receive peak.
Embodiment 2
19mmol 2- methylacryoyloxyethyls Phosphorylcholines and 1mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
12mmol 2- methacryloxyethyls Phosphorylcholines and 8mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued for 24 hours, and after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 10h at 50 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 20h are reacted at 20 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 9.5:0.5, it is configured to the ethanol solution of 0.5mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and
For the mixed solution drop Tu of phosphoryl choline polymer containing sulfydryl on chitosan film surface, the volume of drop coating is 40 μ L/cm2/ face.
It is dried in vacuo for 24 hours at 40 DEG C again.Later, the processing 6h at 50 DEG C is placed in distilled water, you can preparing has imitating cell outer-layer film knot
The crosslinking bionic coating of structure.
Embodiment 3
18mmol 2- methylacryoyloxyethyls Phosphorylcholines and 2mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
8mmol 2- methacryloxyethyls Phosphorylcholines and 12mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 12h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 20h at 30 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 10h are reacted at 30 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 9:1, it is configured to the methanol solution of 2mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain mercapto
For the mixed solution drop Tu of the phosphoryl choline polymer of base on chitosan film surface, the volume of drop coating is 35 μ L/cm2/ face.Again 35
DEG C vacuum drying for 24 hours.Later, the processing 8h at 45 DEG C is placed in distilled water, you can prepares the friendship with imitating cell outer-layer membrane structure
Join bionic coating.
Embodiment 4
16mmol 2- methylacryoyloxyethyls Phosphorylcholines and 4mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
6mmol 2- methacryloxyethyls Phosphorylcholines and 14mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 15h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 18h at 35 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 12h are reacted at 27 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 6:4, it is configured to the ethanol solution of 5mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain mercapto
For the mixed solution drop Tu of the phosphoryl choline polymer of base on chitosan film surface, the volume of drop coating is 25 μ L/cm2/ face.Again 35
DEG C vacuum drying for 24 hours.Later, the processing 12h at 20 DEG C is placed in distilled water, you can prepares the friendship with imitating cell outer-layer membrane structure
Join bionic coating.
Embodiment 5
14mmol 2- methylacryoyloxyethyls Phosphorylcholines and 6mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
9mmol 2- methacryloxyethyls Phosphorylcholines and 11mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 17h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 12h at 45 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 18h are reacted at 22 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 8:2, it is configured to the methanol solution of 10mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain
For the mixed solution drop Tu of the phosphoryl choline polymer of sulfydryl on chitosan film surface, the volume of drop coating is 10 μ L/cm2/ face.Exist again
20 DEG C of vacuum drying are for 24 hours.Later, the processing 11h at 25 DEG C is placed in distilled water, you can is prepared with imitating cell outer-layer membrane structure
It is crosslinked bionic coating.
Embodiment 6
12mmol 2- methylacryoyloxyethyls Phosphorylcholines and 8mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
7mmol 2- methacryloxyethyls Phosphorylcholines and 13mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 22h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 16h at 42 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 11h are reacted at 28 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 7.5:2.5, it is configured to the ethanol solution of 8mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain
There is the mixed solution drop Tu of the phosphoryl choline polymer of sulfydryl on chitosan film surface, the volume of drop coating is 15 μ L/cm2/ face.Again
It is dried in vacuo for 24 hours at 25 DEG C.Later, the processing 10h at 30 DEG C is placed in distilled water, you can preparing has imitating cell outer-layer membrane structure
Crosslinking bionic coating.
Embodiment 7
10mmol 2- methylacryoyloxyethyls Phosphorylcholines and 10mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
7mmol 2- methacryloxyethyls Phosphorylcholines and 13mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 22h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 16h at 42 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 11h are reacted at 28 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 8.5:1.5, it is configured to the methanol solution of 4mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and contain
There is the mixed solution drop Tu of the phosphoryl choline polymer of sulfydryl on chitosan film surface, the volume of drop coating is 37 μ L/cm2/ face.Again
It is dried in vacuo for 24 hours at 27 DEG C.Later, the processing 9h at 38 DEG C is placed in distilled water, you can preparing has imitating cell outer-layer membrane structure
Crosslinking bionic coating.
Embodiment 8
11mmol 2- methylacryoyloxyethyls Phosphorylcholines and 9mmol glycidyl methacrylate are weighed, with
0.1mmol azodiisobutyronitriles are initiator, volume ratio 4:1 methanol and tetrahydrofuran is solvent, under nitrogen protection, 70
For 24 hours, after reaction, concentration of reaction solution is dialysed with the bag filter that molecular cut off is 6000~8000D for DEG C polymerisation, then
It is freeze-dried at -50 DEG C, obtains the phosphoryl choline polymer containing epoxy.
7mmol 2- methacryloxyethyls Phosphorylcholines and 13mmol styrene are weighed, with methanol and tetrahydrofuran
(volume ratio is 4 to mixed solvent:1) dissolving is uniformly mixed and obtains the mixed solution of monomer.In N2It protects, under 70 DEG C of stirring conditions,
By 0.1mmol azodiisobutyronitriles, the mixed solution of monomer is added into three-necked bottle, after preheating 30min, initiator solution is added
The reaction was continued 22h, after reaction, concentration of reaction solution are dialysed with the bag filter that molecular cut off is 6000~8000D, then-
It is freeze-dried at 50 DEG C, obtains the phosphoryl choline polymer containing phenyl ring.
It weighs the 0.2g phosphoryl choline polymer manufactured in the present embodiment containing phenyl ring 30mL chloroforms and methanol mixing is molten
(volume ratio is 1 for agent:1) dissolve, then sequentially add 0.2g zinc chloride, 5mL chloromethyl ethers be uniformly mixed, react 16h at 42 DEG C,
Finally filtering is dried in vacuo for 24 hours at 70 DEG C again.Again by the phosphoryl choline polymer of 0.2g chloromethylations 30mL chloroforms and first
(volume ratio is 1 to alcohol mixed solvent:1) it dissolves, 0.2g NaHSs is then added and are uniformly mixed, 11h are reacted at 28 DEG C, finally
Filtering is dried in vacuo at 70 DEG C obtains the phosphoryl choline polymer containing sulfydryl for 24 hours again.
Phosphoryl choline polymer manufactured in the present embodiment containing epoxy and the phosphoryl choline polymer containing sulfydryl are pressed
Mass ratio 6.5:3.5, it is configured to the methanol solution of 2.5mg/mL.Then by the above-mentioned phosphoryl choline polymer containing epoxy and
For the mixed solution drop Tu of phosphoryl choline polymer containing sulfydryl on chitosan film surface, the volume of drop coating is 27 μ L/cm2/ face.
It is dried in vacuo for 24 hours at 37 DEG C again.Later, the processing 10h at 28 DEG C is placed in distilled water, you can preparing has imitating cell outer-layer film knot
The crosslinking bionic coating of structure.
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, every according to invention skill
Art essence changes any simple modification, change and equivalent structure made by above example, still falls within the technology of the present invention
In the protection domain of scheme.
Claims (10)
1. the method for two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and sulfydryl, feature exist
In including the following steps：
Under nitrogen protection, by the vinyl monomer containing epoxy and the vinyl monomer containing Phosphorylcholine initiator work
Free radical solution polymerization reaction is carried out under, synthesizes the phosphoryl choline polymer containing epoxy；
Under nitrogen protection, the vinyl monomer containing Phosphorylcholine hydrophilic radical, styrene are gathered by Solution Free Radical
It closes, synthesizes the phosphoryl choline polymer containing phenyl ring, and itself and zinc chloride and chloromethyl ether are subjected to chloromethylation, later,
Nucleophilic substitution is carried out with NaHS, you can prepares the phosphoryl choline polymer containing sulfydryl；
Two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are dissolved with polar solvent, and are coated in chitosan film surface,
Dry be placed in distilled water is heated, that is, prepares the crosslinking bionic coating with imitating cell outer-layer membrane structure.
2. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that the vinyl monomer containing Phosphorylcholine hydrophilic radical and the vinyl containing epoxy
Monomer mole ratio is (9.5:0.5)~(5:5).
3. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that the vinyl monomer containing Phosphorylcholine hydrophilic radical and styrene monomer molar ratio
It is (9.5:0.5)~(5:5).
4. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that the vinyl monomer containing Phosphorylcholine hydrophilic radical is methylacryoyloxyethyl
Phosphorylcholine, the vinyl monomer containing epoxy are glycidyl methacrylate.
5. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that in the phosphoryl choline polymer containing epoxy, solvent be methanol and tetrahydrofuran mixed solvent,
Initiator is azodiisobutyronitrile, and reaction temperature is 65~75 DEG C, and the reaction time is 20~26h, is 7000 with molecular cut off
Bag filter dialyse, be freeze-dried at -50 DEG C.
6. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that in chloromethyl reaction, the phosphoryl choline polymer chloroform containing phenyl ring and methanol are mixed molten
Agent is dissolved, and then sequentially adds zinc chloride, chloromethyl ether is uniformly mixed, 10~20h of reaction at 30~50 DEG C；Phosphorus containing phenyl ring
The solid-to-liquid ratio of phatidylcholine polymer and chloromethyl ether is 2g:50ml.
7. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that in sulfydryl nucleophilic substitution, by the phosphoryl choline polymer chloroform and methanol of chloromethylation
Mixed solvent dissolves, and sulfhydrylation sodium is then added and is uniformly mixed, 10~20h is reacted at 20~30 DEG C；The phosphinylidyne of chloromethylation
The mass ratio of choline polymer and sulfhydrylation sodium is 1:1.
8. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that two kinds of phosphoryl choline polymers containing epoxy and sulfydryl are configured to a concentration of 0.5~10mg/
ML solution, for drop Tu on chitosan film surface, the volume of drop coating is 10~40 μ L/cm2/ face.
9. two kinds of phosphoryl choline polymer bionic coating modification of chitosan according to claim 1 containing epoxy and sulfydryl
The method of film, which is characterized in that the polar solvent is methanol or ethyl alcohol.
10. it is poly- that two kinds of phosphoryl choline polymer bionic coatings according to claim 1 containing epoxy and sulfydryl are modified shell
The method of sugared film, which is characterized in that it is that 6~12h is handled in 20~50 DEG C that painting, which is placed on heating temperature in distilled water,.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015021038A (en) * | 2013-07-17 | 2015-02-02 | 日油株式会社 | Phosphorylcholine group-containing polymer and production method thereof |
| CN105288731A (en) * | 2015-11-16 | 2016-02-03 | 西安科技大学 | Method for preparing bionic coating through crosslinking of epoxy group and mercapto group |
| CN107652392A (en) * | 2017-10-09 | 2018-02-02 | 西安科技大学 | A kind of preparation method containing sulfydryl phosphoryl choline polymer |
| CN107722321A (en) * | 2017-10-09 | 2018-02-23 | 西安科技大学 | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and amino |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015021038A (en) * | 2013-07-17 | 2015-02-02 | 日油株式会社 | Phosphorylcholine group-containing polymer and production method thereof |
| CN105288731A (en) * | 2015-11-16 | 2016-02-03 | 西安科技大学 | Method for preparing bionic coating through crosslinking of epoxy group and mercapto group |
| CN107652392A (en) * | 2017-10-09 | 2018-02-02 | 西安科技大学 | A kind of preparation method containing sulfydryl phosphoryl choline polymer |
| CN107722321A (en) * | 2017-10-09 | 2018-02-23 | 西安科技大学 | The method of two kinds of phosphoryl choline polymer bionic coating Chitosan films containing epoxy and amino |
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