CN102391539A - Surface-controlled polymerization modified biological material and preparation method thereof - Google Patents
Surface-controlled polymerization modified biological material and preparation method thereof Download PDFInfo
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- CN102391539A CN102391539A CN 201110246393 CN201110246393A CN102391539A CN 102391539 A CN102391539 A CN 102391539A CN 201110246393 CN201110246393 CN 201110246393 CN 201110246393 A CN201110246393 A CN 201110246393A CN 102391539 A CN102391539 A CN 102391539A
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Abstract
The invention relates to a surface-controlled polymerization modified biological material which comprises a biological material matrix and is characterized in that after the silanization processing is carried out on the biological material, a 'brush'-shaped amphoteric ion polymer layer is grafted on the surface of the biological material. A RATARP (Reverse Atom Transfer Radical Polymerization) complex catalysis system comprising a silane coupling agent and copper halide is adopted by the invention, which is different from 2, 2'- bipyridine (Bpy) ligand adopted in the conventional RATARP (Reverse Atom Transfer Radical Polymerization) reaction, wherein the silane coupling agent is used as the coupling agent and simultaneously is used as a ligand to participate in the RATARP (Reverse Atom Transfer Radical Polymerization) reaction; and a amphoteric ion monomer is grafted on the surface of the biological material through the RATARP (Reverse Atom Transfer Radical Polymerization). According to the invention, the specificity and the functionality of adsorption protein on the surface of the biological material can be effectively regulated and controlled, and the adherence of blood cells and the multi-way activation of blood are inhibited, thereby obtaining the biological material with excellent blood compatibility. The invention also discloses the preparation method of the biological material.
Description
Technical field
The present invention relates to a kind of biomaterial and preparation method thereof; Be particularly related to biomaterial of a kind of surperficial controllable polymerization modification and preparation method thereof, utilize new RATRP catalystsystem, wherein silane coupling agent had both been born the effect of coupling agent; Participate in the RATRP reaction as single part again; Zwitterionic monomer is grafted to surface of polymer material, has realized zwitterionic " activity " controllable polymerization, finally obtain having the biomaterial of good blood compatibility.
Background technology
Along with Biomedical Development, Application of Biomaterial becomes more and more widely with important.At present, for most of medical material, when it contacts with biological tissue, can cause some important reactions, not hope the immunoreation that takes place such as formation and some of thrombus.Biocompatibility, especially blood compatibility are the most important performance index of bio-medical material.The biocompatibility that how to improve biomaterial is the research focus always.The biocompatibility, the research and development biocompatible polymer material that improve macromolecular material have important scientific meaning and huge economic and social benefits.
The research early start of controlled active free radical polymerization is in nineteen eighty-two.Receive much concern owing to having plurality of advantages.So far, three kinds of the most successful active free radical polymerizations are ATRP (ATRP), reversible addition-fracture chain transfer (RAFT), nitrogen oxygen regulation and control radical polymerization (NMP).Wherein use the most extensive with the ATRP method.Polymkeric substance tail end after the forward ATRP termination reaction has active halogen atom.The active halo atom can easily be converted into other functional groups.Except tail end was functional, functional monomer or functional initiator also can be realized the functional polymerization of ATRP.The advantage that this list of tools that is ATRP designs as macromolecular structure reveals, in addition, its synthetic polymericular weight controlled amount, and narrow molecular weight distribution, polymerization technique is simple.
But still there are two shortcomings in ATRP: the poisonous metal catalyst of 2. going back ortho states of 1. used initiator halogenide is difficult for preserving to oxygen or moisture-sensitive.Therefore, reverse atom transfer radical polymerization (RATRP) arises at the historic moment.With at first use the halogenide initiator different among the ATRP of routine, RATRP is radical I or the I-PXMt from general decomposition of initiator
N+1Passivation reaction begin.At initiating stage, initiator radical I forms low-valent transition metals Mt in case generation just can be captured halogen atom from the transition metal halide of high price
nWith dormancy kind I-X, next just the same with conventional ATRP.Its existing ATRP synthetic advantage has been avoided the former shortcoming again.Fig. 5 is the reaction principle synoptic diagram of RATRP.
The RATRP reaction mechanism.
But in the conventional RATRP reaction, generally adopt 2,2 ' dipyridyl (bpy), exist problems such as the part cost is high, toxic as part.Therefore, study RATRP catalystsystem preferably, and be applied to bio-medical material and have important significance for theories and practice significance.
Summary of the invention
In order to overcome the problem that exists in the prior art; The invention provides the biomaterial that a kind of surperficial controllable polymerization is modified; Its surperficial zwitter-ion " activity " controllable polymerization forms the amphoteric ion polymer layer; The specificity of adjustable adhesion protein and functional has the biomaterial surface of good blood compatibility.
Another object of the present invention also is to provide the preparation method of said biomaterial.
In brief; The present invention has designed a kind of new RATRP catalystsystem, and silane coupling agent not only as coupling agent but also as single part participation RATRP reaction, is similar to mantoquita and 2; Effect between 2 '-dipyridyl; In this RATRP reaction, silane coupling agent and mantoquita form 4 co-ordination complexs (as shown in Figure 1), and this complex compound is seized halogen atom by the radical that produces in the RATRP reaction at once; Generate halogenide dormancy kind and metal complex at a low price, and then make zwitterionic monomer (containing the yin, yang ionic group in the molecular structure simultaneously) successfully be grafted to biomaterial surface.
In order to accomplish the foregoing invention task, technical scheme provided by the invention is following:
The biomaterial that a kind of surperficial controllable polymerization is modified comprises the biomaterial matrix, it is characterized in that: after the biomaterial silylanization is handled, and biomaterial surface grafting " brush " shape amphoteric ion polymer layer.
The biomaterial that described surperficial controllable polymerization is modified; Be at biomaterial surface; Utilize a kind of new RATRP complex catalysis system that comprises silane coupling agent and copper halide, wherein silane coupling agent had both been born the effect of coupling agent, again it was participated in the RATRP reaction as single part; Utilize the RATRP reaction that zwitterionic monomer is grafted to biomaterial surface, to realize " activity " controllable polymerization of zwitterionic monomer.
The biomaterial that above-mentioned surperficial controllable polymerization is modified; The preferred tail end of described silane coupling agent contains the silane coupling agent of chlorine, cyanic acid functional groups; Chloromethyl front three (second) TMOS for example; Dichloromethyl front three (second) TMOS, 3-chloropropyl front three (second) TMOS or 2-cyano ethyl front three (second) TMOS.
The biomaterial that above-mentioned surperficial controllable polymerization is modified, described biomaterial (matrix) is the multipolymer of Zylox, urethane or Zylox and urethane; Or Vilaterm, SE, tetrafluoroethylene.
The biomaterial that above-mentioned surperficial controllable polymerization is modified, described zwitterionic monomer can be phosphorus ammonium, sulfanilamide (SN) or carboxylic ammonium zwitter-ion, its structure is distinguished as follows:
Phosphorus ammonium:
Sulfanilamide (SN):
Carboxylic ammonium:
Where R:
or
or
(methacrylate type) (methacrylic acid amino ester type) (styrene type).
Described zwitterionic monomer good biocompatibility; And with the surface of cell membrane material type seemingly; Zwitterionic monomer carries out surface-treated through RATRP reaction pair polymkeric substance; Surface modified arrestin effectively adheres to, and can regulate and control it to proteic adsorptive power through the length of polymerization time, effectively regulates and control the specificity of biomaterial surface adhesion protein and functional.
The invention still further relates to the preparation method of described biomaterial, adopt following technical scheme:
The preparation method of the biomaterial that a kind of surperficial controllable polymerization is modified comprises the following steps:
A. the silylanization of biomaterial is handled: the biomaterial matrix is added in mass percentage concentration 0.05～0.50% silane coupling agent aqueous solution, and magnetic agitation 3～6h, it is dry to take out final vacuum, obtains the biomaterial of silylanization.
B. the biomaterial surface initiator of silylanization is fixing: the biomaterial and 5～15 mL water of silylanization are added in the three-necked flask, and add 0.002～0.02 mL superoxide, room temperature condition stirs 5～10 min down.
C. zwitterionic monomer is at the graft polymerization reaction of silylanization biomaterial surface: the biomaterial that initiator has been fixed on the surface is put into the water or the methanol aqueous solution of 0.1～1 mol/L zwitterionic monomer; And adding copper halide and silane coupling agent part, the ratio of its amount of substance is: M
Zwitter-ion: M
Copper halide: M
The silane coupling agent part=90～120:3～5:7～11, under inert gas atmosphere, stirring at room reaction 1h～72h takes out biomaterial then, and it is dry that water cleans final vacuum.
Above-mentioned preparation method, the preferred chloromethyl front three of described silane coupling agent (second) TMOS, dichloromethyl front three (second) TMOS, 3-chloropropyl front three (second) TMOS, or 2-cyano ethyl front three (second) TMOS.
Described biomaterial is the multipolymer of Zylox, urethane or Zylox and urethane; Or Vilaterm, SE, tetrafluoroethylene.
Above-mentioned preparation method, the said superoxide of step b is preferably Lucidol or tert-butyl peroxide hydrogen.
Above-mentioned preparation method, the described copper halide of step c is preferably CuBr
2Or CuCl
2Zwitterionic monomer is phosphorus ammonium, sulfanilamide (SN) or carboxylic ammonium zwitterionic monomer, and its structure is distinguished as follows:
Phosphorus ammonium:
Sulfanilamide (SN):
Carboxylic ammonium:
Where? R:
or
or
(methacrylate type) (methacrylic acid amino ester type) (styrene type).
The biomaterial that the surperficial controllable polymerization of the present invention's preparation is modified, its surface grafting one deck " brush " shape amphoteric ion polymer layer, the SEM figure of polymer biomaterial sees Fig. 3 a and Fig. 3 b before and after modifying.Can find out from Fig. 3 b, the phosphorus ammonium zwitterionic monomer that novel complex catalysis system causes through the RATRP reaction after, arrange in that the polymer chain of biomaterial surface is orderly regularly, obtain cumulative, a molecule even curface of density; The biomaterial surface that contains the modification of sulfanilamide (SN) or carboxylic ammonium zwitterionic monomer also obtains similar result.
The surface that this zwitterionic monomer is modified arrestin effectively adheres to, and can regulate and control it to proteic adsorptive power (Fig. 2) through the length of polymerization time, and then suppresses the adhesion of hemocyte, finally can improve the blood compatibility of material.Platelet adhesion experiment also draws the conclusion consistent with it: the biological material film surface after the zwitterionic monomer graft modification, platelet adhesion seldom, and thrombocyte almost keeps original form, not distortion (Fig. 4).Explain that " brush " shape amphoteric ion polymer can effectively regulate and control the specificity of biomaterial surface adhesion protein and functional, suppress hemocyte adhesion, suppress the multipath activation of blood.
Beneficial effect of the present invention comprises following aspect at least:
The present invention provides a kind of new RATRP catalystsystem, promptly adopts silane coupling agent, has both born the effect of coupling agent, again it is participated in the RATRP reaction as part, and is controlled at biomaterial surface grafting one deck " brush " shape amphoteric ion polymer layer.
The present invention adopts silane coupling agent to replace 2 of routine; 2 '-dipyridyl is as part; Silane coupling agent can form a kind of 4 new ligand complex catalystsystem with copper halide; Its catalysis RATRP reaction effect is obvious, and compares 2, and 2 '-dipyridyl raw material is easy to get, does not have toxicity, reaction conditions to simplify.
RATRP catalystsystem provided by the invention; Not only successfully realized zwitterionic " activity " controllable polymerization; And can effectively regulate and control the specificity of various biomaterial surface adhesion proteins and functional; Suppress adhesion, the multipath activation of inhibition blood of hemocyte, finally obtain having the biomaterial surface of good blood compatibility.
This new RATRP catalystsystem provided by the invention has been simplified the method for reverse atom transfer radical polymerization, and its compound method is simple, and asepsis environment-protecting is easy to suitability for industrialized production.
The biomaterial of the present invention preparation can be widely used in anticoagulation device (like medical catheter, medical support etc.) aspect, in discharge opeing, and perfusion, dispensing, auxiliary importing medical apparatus such as blood sampling and have application widely at aspects such as human health cares.
Description of drawings
Fig. 1 is the complex catalysis system synoptic diagram that silane coupling agent and copper halide form.
Fig. 2 is that differential responses time aggregation thing biomaterial is to the protein adsorption situation map.
Fig. 3 a and Fig. 3 b are respectively the SEM figure of the polymer biomaterial (b) behind unmodified polymer biomaterial (a) and the grafting zwitterionic monomer.
Fig. 4 is the platelet adhesion figure of grafting zwitterionic monomer artifact material surface.
Fig. 5 is the reaction principle synoptic diagram of RATRP.
Embodiment
Through embodiment the present invention is specifically described below, be necessary to be pointed out that at this, following examples only are used for further specifying of the present invention, can not be interpreted as the restriction to protection domain of the present invention.
Embodiment 1
10 Zylox diaphragms are added in 0.5% (wt%) silane coupling agent chloromethyl triethoxyl silane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 24h obtain the Zylox diaphragm of silylanization.The silicone rubber membrane and the 15mL secondary water of silylanization are added in the three-necked flask, and add 0.02 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 10min.The surface has been fixed the silicone rubber membrane of Lucidol initiator and put into the aqueous solution of 1 mol/L phosphorus ammonium zwitterionic monomer (R is a methacrylate type), and added CuCl
2With silane coupling agent chloromethyl triethoxysilicane alkyl ligand, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
The chloromethyl triethoxyl silane=120:5:11 feeds nitrogen protection then.Stirring reaction 72h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 2
10 Zylox diaphragms are added in 0.05% (wt%) silane coupling agent chloromethyl Trimethoxy silane aqueous solution magnetic agitation 3h.Take out, 110 ℃ of vacuum-drying 24h obtain the Zylox diaphragm of silylanization.The silicone rubber membrane and the 5mL secondary water of silylanization are added in the three-necked flask, and add 0.004 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 5min.The surface has been fixed the silicone rubber membrane of tert-butyl peroxide hydrogen initiator and put into the methanol aqueous solution of 0.1 mol/L phosphorus ammonium zwitterionic monomer (R is a methacrylic acid amino ester type), and added CuBr
2With silane coupling agent chloromethyl Trimethoxy silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The chloromethyl Trimethoxy silane=90:3:7 feeds nitrogen protection then.Stirring reaction 1h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
10 polyurethane diaphragms are added in 0.08% (wt%) silane coupling agent dichloromethyl Trimethoxy silane aqueous solution magnetic agitation 4h.Take out, 110 ℃ of vacuum-drying 24h obtain the polyurethane diaphragm of silylanization.The polyurethane film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.004 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 5min.The surface has been fixed the polyurethane film of tert-butyl peroxide hydrogen initiator and put into the aqueous solution of 0.2 mol/L sulfanilamide (SN) zwitterionic monomer (R is a methacrylic acid amino ester type), and added CuBr
2With silane coupling agent dichloromethyl Trimethoxy silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The dichloromethyl Trimethoxy silane=95:3:7 feeds nitrogen protection then.Stirring reaction 6h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 4
10 polyurethane diaphragms are added in 0.09% (wt%) silane coupling agent dichloromethyl triethoxyl silane aqueous solution magnetic agitation 4h.Take out, 110 ℃ of vacuum-drying 24h obtain the polyurethane diaphragm of silylanization.The polyurethane film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.005 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 6min.The surface has been fixed the polyurethane film of Lucidol initiator and put into the aqueous solution of 0.3mol/L carboxylic ammonium zwitterionic monomer (R is a methacrylic acid amino ester type), and added CuCl
2With silane coupling agent dichloromethyl triethoxysilicane alkyl ligand, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
The dichloromethyl triethoxyl silane=95:4:7 feeds nitrogen protection then.Stirring reaction 12h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 5
10 Zylox-polyurethane copolymer diaphragm is added in 0.09% (wt%) silane coupling agent 3-r-chloropropyl trimethoxyl silane aqueous solution magnetic agitation 5h.Take out, 110 ℃ of vacuum-drying 24h obtain the Zylox-polyurethane copolymer diaphragm of silylanization.Zylox-polyurethane copolymer the film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.006 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 6min.The surface has been fixed the film of Lucidol initiator and put into the aqueous solution of 0.3mol/L carboxylic ammonium zwitterionic monomer (R is a methacrylic acid amino ester type), and added CuCl
2With silane coupling agent 3-r-chloropropyl trimethoxyl silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
The 3-r-chloropropyl trimethoxyl silane=95:4:8 feeds nitrogen protection then.Stirring reaction 18h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 6
10 Zylox-polyurethane copolymer diaphragm is added in 0.09% (wt%) silane coupling agent 3-chloropropyl triethoxysilane aqueous solution magnetic agitation 5h.Take out, 110 ℃ of vacuum-drying 24h obtain the Zylox-polyurethane copolymer diaphragm of silylanization.Zylox-polyurethane copolymer the film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.006 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 6min.The surface has been fixed the film of tert-butyl peroxide hydrogen initiator and put into the aqueous solution of 0.3mol/L phosphorus ammonium zwitterionic monomer (R is a styrene type), and added CuBr
2With silane coupling agent 3-chloropropyl triethoxysilane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The 3-chloropropyl triethoxysilane=95:4:9 feeds nitrogen protection then.Stirring reaction 24h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 7
10 Vilaterm diaphragms are added in 0.1% (wt%) silane coupling agent 2-cyano ethyl Trimethoxy silane aqueous solution magnetic agitation 5h.Take out, 110 ℃ of vacuum-drying 24h obtain the Vilaterm diaphragm of silylanization.The polyethylene film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.007 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 6min.The surface has been fixed the polyethylene film of tert-butyl peroxide hydrogen initiator and put into the aqueous solution of 0.4mol/L phosphorus ammonium zwitterionic monomer (R is a styrene type), and added CuBr
2With silane coupling agent 2-cyano ethyl Trimethoxy silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
2-cyano ethyl Trimethoxy silane=100:4:9 feeds nitrogen protection then.Stirring reaction 30h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 8
10 Vilaterm diaphragms are added in 0.2% (wt%) silane coupling agent 2-cyano ethyl triethoxyl silane aqueous solution magnetic agitation 5h.Take out, 110 ℃ of vacuum-drying 24h obtain the Vilaterm diaphragm of silylanization.The polyethylene film and the 6mL secondary water of silylanization are added in the three-necked flask, and add 0.008 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 6min.The surface has been fixed the polyethylene film of Lucidol initiator and put into the aqueous solution of 0.5mol/L phosphorus ammonium zwitterionic monomer (R is a styrene type), and added CuCl
2With silane coupling agent 2-cyano ethyl triethoxysilicane alkyl ligand, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
2-cyano ethyl triethoxyl silane=100:4:11 feeds nitrogen protection then.Stirring reaction 36h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 9
10 SE diaphragms are added in 0.3% (wt%) silane coupling agent chloromethyl Trimethoxy silane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 24h obtain the SE diaphragm of silylanization.The polychloroethylene film and the 7mL secondary water of silylanization are added in the three-necked flask, and add 0.009 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 7min.The surface has been fixed the polychloroethylene film of Lucidol initiator and put into the aqueous solution of 0.6mol/L phosphorus ammonium zwitterionic monomer (R is a styrene type), and added CuBr
2With silane coupling agent chloromethyl Trimethoxy silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The chloromethyl Trimethoxy silane=100:5:11 feeds nitrogen protection then.Stirring reaction 48h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 10
10 SE diaphragms are added in 0.4% (wt%) silane coupling agent dichloromethyl Trimethoxy silane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 26h obtain the SE diaphragm of silylanization.The polychloroethylene film and the 7mL secondary water of silylanization are added in the three-necked flask, and add 0.01 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 7min.The surface has been fixed the polychloroethylene film of tert-butyl peroxide hydrogen initiator and put into the aqueous solution of 0.6mol/L sulfanilamide (SN) zwitterionic monomer (methacrylic acid amino ester type), and added CuCl
2With silane coupling agent dichloromethyl Trimethoxy silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
The dichloromethyl Trimethoxy silane=110:5:11 feeds nitrogen protection then.Stirring reaction 52h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
10 polytetrafluoroethylene diaphragms are added in 0.5% (wt%) silane coupling agent 2-cyano ethyl triethoxyl silane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 24h obtain the polytetrafluoroethylene diaphragm of silylanization.The poly tetrafluoroethylene and the 8mL secondary water of silylanization are added in the three-necked flask, and add 0.014 mL tert-butyl peroxide hydrogen initiator, the room temperature condition lower magnetic force stirs 8min.The surface has been fixed the poly tetrafluoroethylene of tert-butyl peroxide hydrogen initiator and put into the aqueous solution of 0.7mol/L carboxylic ammonium zwitterionic monomer (methacrylic acid amino ester type), and added CuCl
2With silane coupling agent 2-cyano ethyl triethoxysilicane alkyl ligand, the ratio of its amount of substance is: M
Zwitter-ion: M
CuCl2: M
2-cyano ethyl triethoxyl silane=115:5:11 feeds nitrogen protection then.Stirring reaction 66h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 12
10 polytetrafluoroethylene diaphragms are added in 0.5% (wt%) silane coupling agent 3-chloropropyl triethoxysilane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 24h obtain the polytetrafluoroethylene diaphragm of silylanization.The poly tetrafluoroethylene and the 8mL secondary water of silylanization are added in the three-necked flask, and add 0.016 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 8min.The surface has been fixed the poly tetrafluoroethylene of Lucidol initiator and put into the aqueous solution of 0.9mol/L sulfanilamide (SN) zwitterionic monomer (methacrylate type), and added CuBr
2With silane coupling agent 3-chloropropyl triethoxysilane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The 3-chloropropyl triethoxysilane=118:5:11 feeds nitrogen protection then.Stirring reaction 70h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
Embodiment 13
10 polyurethane diaphragms are added in 0.5% (wt%) silane coupling agent 3-r-chloropropyl trimethoxyl silane aqueous solution magnetic agitation 6h.Take out, 110 ℃ of vacuum-drying 24h obtain the polyurethane diaphragm of silylanization.The polyurethane film and the 9mL secondary water of silylanization are added in the three-necked flask, and add 0.018 mL Lucidol initiator, the room temperature condition lower magnetic force stirs 10min.The surface has been fixed the polyurethane film of Lucidol initiator and put into the aqueous solution of 0.9mol/L phosphorus ammonium zwitterionic monomer (methacrylate type), and added CuBr
2With silane coupling agent 3-r-chloropropyl trimethoxyl silane part, the ratio of its amount of substance is: M
Zwitter-ion: M
CuBr2: M
The 3-r-chloropropyl trimethoxyl silane=119:5:11 feeds nitrogen protection then.Stirring reaction 70h under the room temperature.Take out diaphragm, clean vacuum-drying with a large amount of secondary water.
The foregoing description limits the present invention never in any form, and all employings are equal to the technical scheme of the form acquisition of replacement or equivalent transformation, all drop within protection scope of the present invention.
Claims (10)
1. the biomaterial that surperficial controllable polymerization is modified comprises the biomaterial matrix, it is characterized in that: after the biomaterial silylanization is handled, and biomaterial surface grafting " brush " shape amphoteric ion polymer layer.
2. the biomaterial that surperficial controllable polymerization according to claim 1 is modified; It is characterized in that,, zwitterionic monomer is grafted to biomaterial surface by the RATRP reaction at biomaterial surface; The RATRP complex catalysis system that is adopted comprises silane coupling agent and copper halide; Wherein silane coupling agent is a coupling agent, participates in the RATRP reaction as single part again, at biomaterial surface grafting one deck " brush " shape amphoteric ion polymer layer.
3. the biomaterial that surperficial controllable polymerization according to claim 2 is modified is characterized in that the preparation of described biomaterial may further comprise the steps:
A. the silylanization of biomaterial is handled: the biomaterial matrix is added in mass percentage concentration 0.05～0.50% silane coupling agent aqueous solution, and magnetic agitation 3～6h, it is dry to take out final vacuum, obtains the biomaterial of silylanization;
B. the biomaterial surface initiator of silylanization is fixing: the biomaterial and 5～15 mL water of silylanization are added in the three-necked flask, and add 0.002～0.02 mL superoxide, room temperature condition stirs 5～10 min down;
C. zwitterionic monomer is at the graft polymerization reaction of silylanization biomaterial surface: the biomaterial that initiator has been fixed on the surface is put into the water or the methanol aqueous solution of 0.1～1mol/L zwitterionic monomer; And adding copper halide and silane coupling agent part, the ratio of its amount of substance is: M
Zwitter-ion: M
Copper halide: M
The silane coupling agent part=90～120:3～5:7～11, under inert gas atmosphere, stirring at room reaction 1h～72h takes out biomaterial, and it is dry that water cleans final vacuum.
4. according to the biomaterial of claim 2 or 3 described surperficial controllable polymerizations modifications, it is characterized in that: described silane coupling agent tail end contains chlorine or cyanic acid.
5. the biomaterial that surperficial controllable polymerization according to claim 4 is modified, it is characterized in that: described silane coupling agent is chloromethyl front three (second) TMOS, dichloromethyl front three (second) TMOS, 3-chloropropyl front three (second) TMOS or 2-cyano ethyl front three (second) TMOS.
6. the biomaterial of modifying according to claim 1,2 or 3 described surperficial controllable polymerizations, it is characterized in that: described biomaterial is the multipolymer of Zylox, urethane or Zylox and urethane; Or Vilaterm, SE, tetrafluoroethylene.
7. the biomaterial of modifying according to claim 1,2 or 3 described surperficial controllable polymerizations, it is characterized in that: described zwitterionic monomer is phosphorus ammonium, sulfanilamide (SN) or carboxylic ammonium zwitter-ion, its structure is distinguished as follows:
Phosphorus ammonium:
Sulfanilamide (SN):
Carboxylic ammonium:
Where R:
or
or
.
8. the preparation method of the biomaterial of a surperficial controllable polymerization modification comprises the following steps:
A. the silylanization of biomaterial is handled: the biomaterial matrix is added in mass percentage concentration 0.05～0.50% silane coupling agent aqueous solution, and magnetic agitation 3～6h, it is dry to take out final vacuum, obtains the biomaterial diaphragm of silylanization;
B. the biomaterial surface initiator of silylanization is fixing: the biomaterial and 5～15 mL water of silylanization are added in the three-necked flask, and add 0.002～0.02 mL superoxide, room temperature condition stirs 5～10 min down;
C. zwitterionic monomer is at the graft polymerization reaction of silylanization biomaterial surface: the biomaterial that initiator has been fixed on the surface is put into the water or the methanol aqueous solution of 0.1～1 mol/L zwitterionic monomer; And adding copper halide and silane coupling agent part, the ratio of its amount of substance is: M
Zwitter-ion: M
Copper halide: M
The silane coupling agent part=90～120:3～5:7～11, under inert gas atmosphere, stirring at room reaction 1h～72h takes out biomaterial then, and it is dry that water cleans final vacuum.
9. preparation method according to claim 8 is characterized in that: described silane coupling agent is chloromethyl front three (second) TMOS, dichloromethyl front three (second) TMOS, 3-chloropropyl front three (second) TMOS or 2-cyano ethyl front three (second) TMOS;
Described biomaterial is the multipolymer of Zylox, urethane or Zylox and urethane, or Vilaterm, SE, tetrafluoroethylene;
Described zwitterionic monomer is phosphorus ammonium, sulfanilamide (SN) or carboxylic ammonium zwitterionic monomer, and its structure is distinguished as follows:
Phosphorus ammonium:
Sulfanilamide (SN):
Carboxylic ammonium:
Where R:
? or
? or
.
10. preparation method according to claim 8 is characterized in that: the said superoxide of step b) is Lucidol or tert-butyl peroxide hydrogen; The described copper halide of step c) is CuBr
2Or CuCl
2
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