CN104018198A - Method for modifying surface of metal material by using phenolic derivative amino polysaccharide polymer by virtue of electrochemical method - Google Patents
Method for modifying surface of metal material by using phenolic derivative amino polysaccharide polymer by virtue of electrochemical method Download PDFInfo
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- CN104018198A CN104018198A CN201410254519.2A CN201410254519A CN104018198A CN 104018198 A CN104018198 A CN 104018198A CN 201410254519 A CN201410254519 A CN 201410254519A CN 104018198 A CN104018198 A CN 104018198A
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Abstract
The invention provides a method for modifying the surface of a metal material by using a phenolic derivative amino polysaccharide polymer by virtue of an electrochemical method, belonging to the technical field of metal surface modification. The method comprises the following steps: preparing the phenolic derivative amino polysaccharide polymer by use of the Mannich method; by adopting a triple-electrode system, immersing the metal material to be modified in an appropriate alkaline buffer solution, and then carrying out an electrochemical reaction of an anode, namely the metal material in an electrolytic tank so that the metal material is electrochemically modified by a medium in the solution, thereby obtaining the modified metal material having excellent biocompatibility and antibacterial property. Compared with the traditional coating modification process having the defects such as long modification time, poor coating adhesion, uneven surface and the like, the method is mainly characterized in that the coating time can be greatly shortened, the obtained coating is evener and more compact and stronger in adhesion, and meanwhile, secondary modification, for example, sulfonation reaction and the like, can be carried out, so that the physical and chemical properties of the surface of the material can be improved.
Description
Technical field
The present invention is by a kind of phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process, and then adopts electrochemical process to improve biocompatibility and the germ resistance of metal material surface, belongs to Metal Surface Modification Technique field.
Background technology
Electrochemical method is to take initiation power and the motivating force that electropotential is polyreaction, makes monomer in electrode surface direct polymerization film forming.Electrochemical method is fairly simple, and it has advantages of that some are unique: (1) polymerization and doping are carried out simultaneously; (2) can generate in electrode previous step the conducting film of self-supporting; (3) by changing polymerization potential, can distinguish easily the redox state of controlling diaphragm; (4) thickness of film can be controlled by electric weight; (5) product is without separating step; (6) on electrode, generating the process of polymkeric substance or the polymkeric substance of generation can study by electrochemistry or spectral method easily, without catalyzer etc., has therefore obtained broad research.Electrochemical method comprises cyclic voltammetry, potentiostatic method, galvanostatic method etc.In electrochemical method, cathode reduction method is because the conductivity of the conducting polymer film obtaining at electrode surface is poor, and film thickness is difficult to surpass 100nm; So research is fewer.Therefore electrochemical method generally refers to anonizing.
The glycosaminoglycan such as chitosan, heparin, has the required stability of pharmaceutical preparation auxiliary material, solvability, viscosity and security, in the solution after chitosan dissolving simultaneously, contains amino (NH2
+), these amino are by coming anti-bacteria to show germ resistance in conjunction with negatron.They demonstrate multiple important physiological function with its unique molecular structure and physico-chemical property in body, as lubricated joint, regulate the permeability of vessel wall, regulate protein, anticoagulation, and Water-Electrolyte diffusion and running, promote wound healing etc.Thereby they can be used as timbering material for medical usage, possess good biocompatibility and germ resistance.
At present, though it is multiple that the process for modifying surface of medical stainless steel has, as ion implantation, differential arc oxidation, plasma technique etc., also do not have a kind of method can meet clinical requirement completely, as surface reforming layer and substrate combinating strength not high, biocompatibility is strong not etc.Pyrocatechol is a kind of very important derivative of phenol derivatives, and its majority is present in occurring in nature with the form of derivative, is the earliest to be obtained by destructive distillation Protocatechuic Acid or distillation catechu extracting solution.And phenol is early for a kind of important phenol derivatives of electrochemical research.At present people mostly utilize solution soaking method (dipping coating) by phenol derivatives as Dopamine HCL film forming on metallic substance.This method mild condition, but film formation time is longer, conventionally needs 24 hours, and this method also faces the problems such as strength of coating, sticking power and fraction of coverage in addition.And pass through Mannich legal system for amphyl-glycosaminoglycan polymkeric substance, further by electrochemical method, be coated on medical metal material, can significantly improve the performance of coating, and to improving biocompatibility, blood compatibility, germ resistance and the erosion resistance etc. of embedded type metallic substance, to improving success rate of operation and minimizing patient's misery, there is very important realistic meaning.
Summary of the invention
The defect existing for prior art, the object of the present invention is to provide a kind of method of phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process.Mannich legal system is carried out to electrochemical modification to metallic surface for phenol derivatives-glycosaminoglycan polymkeric substance of electrodepositable in electrolyzer, obtain the metallic substance that biocompatibility and germ resistance are good.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process, Mannich legal system is carried out to electrochemical modification to metallic surface for phenol derivatives-glycosaminoglycan polymkeric substance of electrodepositable in electrolyzer, and specific embodiment and step are as follows:
(1) under room temperature, take 500 ~ 5000mg glycosaminoglycan polymkeric substance, 50 ~ 500mg paraformaldehyde, 500 ~ 4000mg phenol and derivative thereof, be dissolved in 10 ~ 40ml, 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h;
(2) use extraction using alcohol reaction product, lyophilize obtains phenol derivatives-glycosaminoglycan polymkeric substance;
(3) get in Tris-HCl (Tutofusin tris-hydrochloric acid) damping fluid that appropriate phenol derivatives-glycosaminoglycan polymkeric substance is dissolved in 30 ~ 50ml pH=8.0; Adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), and platinum post electrode is to electrode (negative electrode), and saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction; The required reaction times is 10 ~ 20min, and reaction optimum voltage is 800-1200mv;
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings;
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution sulfonation 1 ~ 2h;
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Described glycosaminoglycan polymkeric substance is chitosan, or amino-α, beta, gamma-cyclodextrin, or ammonia polyose of candy, or mucopolysaccharide, or proteoglycan.
Described phenol derivatives is pyrocatechol, or Resorcinol, or Resorcinol, or phenol.
Described phenol derivatives-glycosaminoglycan polymkeric substance is grafting medium, and coating method is electrochemical method.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and significantly a little:
The inventive method is carried out electrochemical modification to metallic surface for phenol derivatives-glycosaminoglycan polymkeric substance of electrodepositable by Mannich legal system in electrolyzer, obtains the metallic substance that biocompatibility and germ resistance are good.Can greatly shorten coating time, and the coating obtaining is more even, fine and close, sticking power is stronger.Can also carry out twice-modifiedly simultaneously, as sulfonation reaction etc., improve material surface physical and chemical performance.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is reforming apparatus schematic diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.
As shown in Figure 2, the reforming apparatus that the inventive method is used, adopt three-electrode system, by the metallic substance for the treatment of modification, be working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, has modification liquid and electrode device containing phenol derivatives-glycosaminoglycan polymkeric substance in electrolyzer.
Embodiment 1
As shown in Figure 1, a kind of method that metal material surface Quick uniform is applied to phenol derivatives-glycosaminoglycan polymkeric substance.Mannich legal system is carried out to electrochemical modification to metallic surface for phenol derivatives-glycosaminoglycan polymkeric substance of electrodepositable in electrolyzer, and specific embodiment is:
(1) under room temperature, take 1000mg chitosan, 50mg paraformaldehyde, 1000mg pyrocatechol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains pyrocatechol-chitosan polymer.
(3) get in the Tris-HCl damping fluid that appropriate pyrocatechol-chitosan polymer is dissolved in 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 2
(1) under room temperature, take 1000mg amino-α, beta, gamma-cyclodextrin, 50mg paraformaldehyde, 1000mg pyrocatechol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains pyrocatechol-amino-α, beta, gamma-cyclodextrin.
(3) get appropriate pyrocatechol-amino-α, β, γ-cyclodextrin polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), and platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 3
(1) under room temperature, take 1000mg ammonia polyose of candy, 50mg paraformaldehyde, 1000mg pyrocatechol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains pyrocatechol-ammonia polyose of candy polymkeric substance.
(3) getting appropriate pyrocatechol-ammonia polyose of candy polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 4
(1) under room temperature, take 1000mg mucopolysaccharide, 50mg paraformaldehyde, 1000mg pyrocatechol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains pyrocatechol-ammonia polyose of candy polymkeric substance.
(3) getting appropriate pyrocatechol-ammonia polyose of candy polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 5
(1) under room temperature, take 1000mg chitosan, 50mg paraformaldehyde, 1000mg Resorcinol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains Resorcinol-chitosan polymer.
(3) get in the Tris-HCl damping fluid that appropriate Resorcinol-chitosan polymer is dissolved in 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 6
(1) under room temperature, take 1000mg amino-α, beta, gamma-cyclodextrin, 50mg paraformaldehyde, 1000mg Resorcinol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains Resorcinol-amino-α, beta, gamma-cyclodextrin.
(3) get appropriate Resorcinol-amino-α, β, γ-cyclodextrin polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), and platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 7
(1) under room temperature, take 1000mg ammonia polyose of candy, 50mg paraformaldehyde, 1000mg Resorcinol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains Resorcinol-ammonia polyose of candy polymkeric substance.
(3) getting appropriate Resorcinol-ammonia polyose of candy polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Embodiment 8
(1) under room temperature, take 1000mg mucopolysaccharide, 50mg paraformaldehyde, 1000mg Resorcinol, is dissolved in 20ml 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h.
(2) use extraction using alcohol reaction product, lyophilize obtains Resorcinol-ammonia polyose of candy polymkeric substance.
(3) getting appropriate Resorcinol-ammonia polyose of candy polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the electro-conductive material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction, the reaction times required for the present invention is 10 ~ 20min, and reaction optimum voltage is 800-1200mv.
(4) take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings.
(5) by the aqueous cleaning several that contains 75% acetone for above-mentioned materials, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h.
(6) take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
Claims (3)
1. a method for phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process, is characterized in that having following process and step:
A. under room temperature, take 500 ~ 1000mg glycosaminoglycan polymkeric substance, 50 ~ 500mg paraformaldehyde, 500 ~ 1000mg phenol derivatives, is dissolved in 10 ~ 40ml, 0.1 M hydrochloric acid soln, and three mixes at 60 ℃ and stirs 10 ~ 14h;
B. use extraction using alcohol reaction product, lyophilize obtains phenol derivatives-glycosaminoglycan polymkeric substance;
C. getting appropriate amphyl-glycosaminoglycan polymkeric substance is dissolved in the Tris-HCl damping fluid of 30 ~ 50ml pH=8.0, adopt three-electrode system, the metallic conduction material for the treatment of modification is working electrode (anode), platinum post electrode is to electrode (negative electrode), saturated calomel electrode is reference electrode, in electrolyzer Anodic generation electrochemical reaction; The required reaction times is 10 ~ 20min, and reaction optimum voltage is 800-1200mv;
D. take out the electro-conductive material of above-mentioned modification, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, be immersed in the acetone soln of a certain amount of maleic anhydride, 10 ~ 12h under 40 ℃ of stirrings;
E. above-mentioned materials is used to the aqueous cleaning several that contains 75% acetone, then be immersed in certain density S-WAT or sodium sulfite solution 1 ~ 2h;
F. take out metallic substance, be immersed in deionized water for ultrasonic 10 ~ 15min, take out nature and dry, obtain the modified metal material that biocompatibility and germ resistance are good.
2. a kind of method of phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process according to claim 1, is characterized in that, described phenol derivatives is pyrocatechol, or Resorcinol, or Resorcinol, or phenol.
3. a kind of method of phenol derivatives-glycosaminoglycan polymer modification metal material surface for electrochemical process according to claim 1, is characterized in that, described glycosaminoglycan polymkeric substance is chitosan, or amino-α, beta, gamma-cyclodextrin, or ammonia polyose of candy, or mucopolysaccharide, or proteoglycan.
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| CN105036326A (en) * | 2015-08-28 | 2015-11-11 | 浙江工商大学 | Preparation method of reactive membrane electrode with direct electron transfer mechanism |
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| US20090101512A1 (en) * | 2007-10-17 | 2009-04-23 | Kansai Paint Co., Ltd. | Method for forming multilayer coating film and coated article |
| CN103255456A (en) * | 2013-05-13 | 2013-08-21 | 上海大学 | Method for quickly coating polysaccharide polymer on metal material surface |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111273A (en) * | 2004-11-26 | 2008-01-23 | 斯坦托米克斯公司 | Chelating and binding chemicals to a medical implant, medical device formed, and therapeutic applications |
| US20090101512A1 (en) * | 2007-10-17 | 2009-04-23 | Kansai Paint Co., Ltd. | Method for forming multilayer coating film and coated article |
| CN103255456A (en) * | 2013-05-13 | 2013-08-21 | 上海大学 | Method for quickly coating polysaccharide polymer on metal material surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105036326A (en) * | 2015-08-28 | 2015-11-11 | 浙江工商大学 | Preparation method of reactive membrane electrode with direct electron transfer mechanism |
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