CN107417805A - A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface - Google Patents

A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface Download PDF

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Publication number
CN107417805A
CN107417805A CN201710341858.8A CN201710341858A CN107417805A CN 107417805 A CN107417805 A CN 107417805A CN 201710341858 A CN201710341858 A CN 201710341858A CN 107417805 A CN107417805 A CN 107417805A
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preparation
dex
magnesium alloy
electroactive
solution
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刘晓亚
崔燕
朱叶
顾瑶
孙家娣
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Jiangnan University
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications

Abstract

The present invention relates to a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface.The preparation method includes:The Tetraaniline of parents' macromolecular and doped hydrochloride is prepared first, then both are dissolved in good solvent, adds dropwise precipitating reagent, obtains compound self-organized colloidal particle solution;Compound self-organized colloidal particle is finally fixed on Mg alloy surface and forms coating material;The method is easy to operate, applied widely, and a kind of new approaches are provided for the preparation of magnesium-based corrosion-inhibiting coating.

Description

A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface
Technical field
The present invention relates to large biological molecule and the compound self assembly of electroactive oligomer nonaqueous phase and its in Mg alloy surface shape Into the preparation method of coating, belong to macromolecular self-assembly and bio-medical material preparation field.
Technical background
Magnesium alloy has an excellent biocompatibility as new medical metal material, biodegradability and suitable Mechanical performance, it is set to have potential application on medical embedded material.Although magnesium and magnesium alloy have as medical graft materials Many advantages, but active chemical property causes it easily to be degraded under physiological environment, and this defect seriously constrains magnesium And the application of magnesium alloy clinically.Increase its practicality to regulate and control the degradation rate of magnesium and magnesium alloy, generally it is carried out Surface coated treatment.Conventional surface-coating technology has (the J BIOMED such as electrodeposition process, direct dip coating, micro-arc oxidation MATER RES B, 2015,103,342-354).Wherein electro-deposition techniques as a kind of more convenient and economic method, Had a wide range of applications in biological coating preparation process.For natural macromolecular because it has good biocompatibility, biology can Degradability, wide material sources and paid close attention to by research worker.Glucan (Dextran) is thin by what is cultivated in sucrose solution A kind of bacterium, the polysaccharide natural macromolecular for being fermented to obtain by enzymatic, has preferable stability to temperature and pH, its Main purposes is in terms of blood substitutes, is used more in all kinds of shocks.Due to having three on the single sugared ring of glucan Hydroxyl, chemism is high, can meet that the amphiphilic Portugal of different demands gathers by being modified modification to glucan to prepare Sugared functional derivative.Haiping Li et al. access peptide on large biological molecule glucan (Dex) surface, and it is big to form parents Molecule, succeed self assembly in aqueous, obtains the nano-particle PDDNs with core shell structure, result of study shows, preparation Particle no cytotoxicity, have in medicament transport potential using (Polym.Chem., 2013,4,2235-2238);Koji Parents macromolecular dextran-CCM is prepared in dextran surface access curcumin (CCM) in Nagahama et al., in the aqueous solution Middle success self assembly obtains nano-particle, and the nano-particle can be successfully entered in HeLa cell, has in treatment of cancer potential Using (Bioorg.Med.Chem.Lett., 2015,25,2519-2522).At present for glucan self-organized colloidal particle Study more, but the function self-organized colloidal particle based on glucan is also rarely reported for biological coating field.
The self assembly behavioral study of glucan is only limited to aqueous phase at present, and aqueous phase self assembly is unfavorable in Mg alloy surface system Standby coating, therefore this project realizes the nonaqueous phase self assembly of glucan, and colloidal particle is fixed on into magnesium alloy after assembling Surface, biological nano coating is prepared, improve the decay resistance of magnesium alloy.
The content of the invention
A kind of invention preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, this method operation letter It is single, mild condition.I.e. by modified natural polysaccharide, the self assembly in selective solvent is prepared with electroactive small molecule first Composite colloid particle solution, above-mentioned particle is then fixed on by Mg alloy surface by process for treating surface, prepares biological coating Material.
The present invention adopts the following technical scheme that:
A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, its characterization step are:
(1) preparation of parents' macromolecular:Weigh appropriate glucan (Dex) to be dissolved in dimethyl sulfoxide (DMSO), formed equal One solution;Weigh appropriate small molecule caffeic acid (CA) to be dissolved in DMSO, and sequentially add proper catalyst 1- ethyls-(3- bis- Dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) and DMAP (DMAP), activate 10min;Finally will Dex solution is added in CA solution, and the mixed liquor reacts 24h at room temperature, and reaction adds precipitating reagent after terminating, and product is precipitated and analysed Go out, dialysed in deionized water, dialyzate freeze-drying, obtain parents' macromolecular Dex-CA;
(2) synthesis of Tetraaniline:Weigh the mixing that 5.50g 4-aminodiphenylamines are dissolved in acetone and watery hydrochloric acid Being stirred in solution, under ice bath makes it be completely dissolved to obtain solution A;Equivalent ammonium persulfate is dissolved in acetone and deionized water mixed solution In, stirring is completely dissolved it, is then added drop-wise to vigorous stirring in solution A, continues ice bath reaction 4h.Product carry out from The heart, and washed with 0.1mol/L watery hydrochloric acid and acetone, 48h is dried in an oven obtains the Tetraaniline of acid doping;
(3) preparation of compound self-organized colloidal particle solution:Appropriate Dex-CA and Tetraaniline TANi is weighed, is dissolved in good In solvent DMSO, under agitation, precipitating reagent is added dropwise dropwise into above-mentioned solution, promotes Dex-CA/TANi to occur from group Dress, obtains compound self-organized colloidal particle solution;
(4) preparation of coating of magnesium alloy surface:2000 mesh sand paper used for magnesium alloy is polishing to non-oxidation layer, successively anhydrous It is cleaned by ultrasonic 10~15min in ethanol, acetone, room temperature dries standby, then will to be prepared in step (3) self-organized colloidal particle Mg alloy surface is fixed on by electrophoretic deposition technique, obtains the coating material based on the compound self-organized colloidal particle of glucan.
Dex molecular weight is respectively 20,000 and 40,000 in step (1), Dex, CA, EDC, and the ratio between DMAP mole is respectively 1:1:1:1,1:2:2:2,1:3:3:3,1:6:6:6.
In step (3) Dex-CA initial concentration scope be 1~20mg/mL, TANi concentration range be 0.05~ 0.5mg/mL, precipitating reagent are selected from absolute ethyl alcohol, acetone, dioxane, isopropanol, ethyl acetate, tetrahydrofuran, n-butanol, 1- One kind in octanol, there is hydrogen bond and electrostatic interaction between Dex-CA and TANi;The size range of self-assembled micelle particle For 100~400nm.
The species of magnesium alloy is one kind in AZ31, AZ91, AM60B, AM50A, magnesium calcium alloy in step (4), and deposition is electric Pressure scope is 100~200V, and sedimentation time is 0.5~30min.The electroactive coating being prepared and parents' macromolecular system of the same race Standby electrically inactive coating is compared, and has more preferable antiseptic effect.
Main advantages of the present invention are:Self assembly of the glucan in nonaqueous phase is realized, has expanded the self assembly of glucan Behavior;Electroactive small molecule is introduced into self-organized colloidal particle simultaneously, and will be certainly by simple process for treating surface Assembling colloidal particle is fixed on Mg alloy surface, and electroactive corrosion-inhibiting coating is prepared, and simple to operate, material source is extensive, real It is relatively low to test cost.
Brief description of the drawings
The compound self-organized colloidal particle TEM figures of Dex-CA/TANi in Fig. 1 embodiments 1.
The CV curves of the compound self-organized colloidal particles of Dex-CA/TANi in Fig. 2 embodiments 1.
The SEM shape appearance figures of Mg alloy surface biological coating in Fig. 3 embodiments 2.
The polarization curve of Mg alloy surface biological coating in Fig. 4 embodiments 3.
Embodiment
The invention will be further described with reference to embodiments, but the invention is not limited in this.
Embodiment 1
A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, specific implementation step are as follows:
(1) preparation of parents' macromolecular:Weigh 0.172g glucans Dex to be dissolved in 5mL dimethyl sulfoxides (DMSO), formed Uniform solution;Weigh 0.541g caffeic acids CA to be dissolved in DMSO, and sequentially add 0.466g catalyst 1- ethyls-(3- diformazans Base aminopropyl) carbodiimide hydrochloride (EDC.HCl) and 0.367g DMAPs (DMAP), activate 10 min;Most Dex solution is added in above-mentioned CA solution afterwards, the mixed liquor reacts 24h at room temperature, and reaction adds precipitating reagent after terminating, will produced Thing Precipitation, dialyses in deionized water, dialyzate freeze-drying, obtains parents' macromolecular Dex-CA;
(2) synthesis of Tetraaniline:Weigh the mixing that 5.50g 4-aminodiphenylamines are dissolved in acetone and watery hydrochloric acid Being stirred in solution, under ice bath makes it be completely dissolved to obtain solution A;Equivalent ammonium persulfate is dissolved in acetone and deionized water mixed solution In, stirring is completely dissolved it, is then added drop-wise to vigorous stirring in solution A, continues ice bath reaction 4h.Product carry out from The heart, and washed with 0.1mol/L watery hydrochloric acid and acetone, 48h is dried in an oven obtains the Tetraaniline of acid doping;
(3) preparation of compound self-organized colloidal particle solution:0.05g Dex-CA and 1mg Tetraaniline TANi are weighed, It is dissolved in 10mL good solvents DMSO, under agitation, precipitating reagent ethanol is added dropwise dropwise into above-mentioned solution, promotes Dex- Self assembly occurs for CA/TANi, obtains compound self-organized colloidal particle solution, shape appearance figure of the particle under the dry state such as institute of accompanying drawing 1 Show, compound particle it is electroactive as shown in Figure 2;
(4) preparation of coating of magnesium alloy surface:2000 mesh sand paper used for magnesium alloy is polishing to non-oxidation layer, successively anhydrous It is cleaned by ultrasonic 10~15min in ethanol, acetone, room temperature dries standby, then will to be prepared under 200V in step (3) self assembly Colloidal particle is fixed on Mg alloy surface by electrophoretic deposition technique, sedimentation time 5min, finally gives and is answered based on glucan Close the coating material of self-organized colloidal particle.
Embodiment 2
A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, specific implementation step are as follows:
(1) preparation of parents' macromolecular:Weigh 0.172g glucans Dex to be dissolved in 5mL dimethyl sulfoxides (DMSO), formed Uniform solution;Weigh 0.180g caffeic acids to be dissolved in DMSO, and sequentially add 0.155g catalyst 1- ethyls-(3- dimethyl Aminopropyl) carbodiimide hydrochloride (EDC.HCl) and 0.122g DMAPs (DMAP), activate 10min;Finally Dex solution is added in CA solution, the mixed liquor reacts 24h at room temperature, and reaction adds precipitating reagent after terminating, product is precipitated Separate out, dialysed in deionized water, dialyzate freeze-drying, obtain parents' macromolecular Dex-CA;
(2) synthesis of Tetraaniline:Weigh the mixing that 5.50g 4-aminodiphenylamines are dissolved in acetone and watery hydrochloric acid Being stirred in solution, under ice bath makes it be completely dissolved to obtain solution A;Equivalent ammonium persulfate is dissolved in acetone and deionized water mixed solution In, stirring is completely dissolved it, is then added drop-wise to vigorous stirring in solution A, continues ice bath reaction 4h.Product carry out from The heart, and washed with 0.1mol/L watery hydrochloric acid and acetone, 48h is dried in an oven obtains the Tetraaniline of acid doping;
(3) preparation of compound self-organized colloidal particle solution:0.1g Dex-CA and 1mg Tetraanilines TANi is weighed, it is molten In 10mL good solvents DMSO, under agitation, precipitating reagent ethanol is added dropwise dropwise into above-mentioned solution, promotes Dex-CA/ Self assembly occurs for TANi, obtains compound self-organized colloidal particle solution;
(4) preparation of coating of magnesium alloy surface:2000 mesh sand paper used for magnesium alloy is polishing to non-oxidation layer, successively anhydrous It is cleaned by ultrasonic 10~15min in ethanol, acetone, room temperature dries standby, then will to be prepared under 150V in step (3) self assembly Colloidal particle is fixed on Mg alloy surface by electrophoretic deposition technique, sedimentation time 10min, finally gives and is answered based on glucan The coating material of self-organized colloidal particle is closed, the SEM shape appearance figures of coating are as shown in Figure 2.
Embodiment 3
A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, specific implementation step are as follows:
(1) preparation of photosensitive parents' macromolecular:0.172g glucans Dex is weighed to be dissolved in 5mL dimethyl sulfoxides (DMSO), Form uniform solution;Weigh 1.081g caffeic acids CA to be dissolved in DMSO, and sequentially add 0.931g catalyst 1- ethyls-(3- Dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) and 0.733g DMAPs (DMAP), activation 10min;Finally Dex solution is added in CA solution, the mixed liquor reacts 24h at room temperature, and reaction adds precipitating reagent after terminating, By product Precipitation, dialysed in deionized water, dialyzate freeze-drying, obtain parents' macromolecular Dex-CA;
(2) synthesis of Tetraaniline:Weigh the mixing that 5.50g 4-aminodiphenylamines are dissolved in acetone and watery hydrochloric acid Being stirred in solution, under ice bath makes it be completely dissolved to obtain solution A;Equivalent ammonium persulfate is dissolved in acetone and deionized water mixed solution In, stirring is completely dissolved it, is then added drop-wise to vigorous stirring in solution A, continues ice bath reaction 4h.Product carry out from The heart, and washed with 0.15mol/L watery hydrochloric acid and acetone, 48h is dried in an oven obtains the Tetraaniline of acid doping;
(3) preparation of compound self-organized colloidal particle solution:0.15g Dex-CA and 1mg Tetraaniline TANi are weighed, It is dissolved in 10mL good solvents DMSO, under agitation, precipitating reagent isopropanol is added dropwise dropwise into above-mentioned solution, promotes Dex- Self assembly occurs for CA/TANi, obtains compound self-organized colloidal particle solution;
(4) preparation of coating of magnesium alloy surface:2000 mesh sand paper used for magnesium alloy is polishing to non-oxidation layer, successively anhydrous It is cleaned by ultrasonic 10~15min in ethanol, acetone, room temperature dries standby, then will to be prepared under 175V in step (3) self assembly Colloidal particle is fixed on Mg alloy surface by electrophoretic deposition technique, sedimentation time 5min, finally gives and is answered based on glucan Close the coating material of self-organized colloidal particle, the polarization curve such as institute of accompanying drawing 3 of electroactive coating, naked magnesium and simple Dex-CA coatings Show.Above-described embodiment is used for illustrating the present invention, rather than limits the invention, will in the spirit and right of the present invention In the protection domain asked, to any modifications and changes of the invention made, protection scope of the present invention is both fallen within.

Claims (5)

1. a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface, its characterization step are:
(1) preparation of parents' macromolecular:Weigh appropriate glucan (Dex) to be dissolved in dimethyl sulfoxide (DMSO), formed homogeneous molten Liquid;Weigh appropriate small molecule caffeic acid (CA) to be dissolved in DMSO, and sequentially add proper catalyst 1- ethyls-(3- dimethyl Aminopropyl) carbodiimide hydrochloride (EDC.HCl) and DMAP (DMAP), activate 10min;It is finally that Dex is molten Liquid is added in CA solution, and the mixed liquor reacts 24h at room temperature, and reaction adds precipitating reagent after terminating, by product Precipitation, in Dialysed in deionized water, dialyzate freeze-drying, obtain parents' macromolecular Dex-CA;
(2) synthesis of Tetraaniline:Weigh the mixed solution that 5.50g 4-aminodiphenylamines are dissolved in acetone and watery hydrochloric acid In, being stirred under ice bath makes it be completely dissolved to obtain solution A;Equivalent ammonium persulfate is dissolved in acetone and deionized water mixed solution, Stirring is completely dissolved it, is then added drop-wise to vigorous stirring in solution A, continues ice bath reaction 4h.Product is centrifuged, and Washed with 0.1mol/L watery hydrochloric acid and acetone, dry 48h in an oven and obtain the Tetraaniline of acid doping;
(3) preparation of compound self-organized colloidal particle solution:Appropriate Dex-CA and Tetraaniline TANi is weighed, is dissolved in good solvent In DMSO, under agitation, precipitating reagent is added dropwise dropwise into above-mentioned solution, promotes Dex-CA/TANi that self assembly occurs, obtain Compound self-organized colloidal particle solution;
(4) preparation of coating of magnesium alloy surface:2000 mesh sand paper used for magnesium alloy is polishing to non-oxidation layer, successively in anhydrous second It is cleaned by ultrasonic 10~15min in alcohol, acetone, room temperature is dried standby, then leads to the self-organized colloidal particle prepared in step (3) Cross electrophoretic deposition technique and be fixed on Mg alloy surface, obtain the coating material based on the compound self-organized colloidal particle of glucan.
2. according to a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface described in claim 1, its feature exists In Dex molecular weight is respectively 20,000 and 40,000 in step (1), and Dex, CA, EDC, the ratio between DMAP mole is respectively 1:1:1: 1,1:2:2:2,1:3:3:3,1:6:6:6.
3. according to a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface described in claim 1, its feature exists In, in step (3) Dex-CA initial concentration scope be 1~20mg/mL, TANi concentration range be 0.05~0.5mg/mL, Precipitating reagent in absolute ethyl alcohol, acetone, dioxane, isopropanol, ethyl acetate, tetrahydrofuran, n-butanol, 1- octanols one Kind, there is hydrogen bond and electrostatic interaction between Dex-CA and TANi.
4. according to a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface described in claim 1, its feature exists In the size range of self-assembled micelle particle is 100~500nm in step (3).
5. according to a kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface described in claim 1, its feature exists In, in step (4) species of magnesium alloy be AZ31, AZ91, AM60B, AM50A, one kind in magnesium calcium alloy, deposition voltage scope For 100~200V, sedimentation time is 0.5~30min, and the electroactive coating being prepared prepares non-with parents' macromolecular of the same race Electroactive coating is compared, and has more preferable antiseptic effect.
CN201710341858.8A 2017-05-16 2017-05-16 A kind of preparation method of the electroactive corrosion-inhibiting coating of medical magnesium alloy surface Pending CN107417805A (en)

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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102657873A (en) * 2012-05-21 2012-09-12 苏州大学 Vesicles consisting of amphiphilic polymer and application of vesicles
CN103757683A (en) * 2014-01-07 2014-04-30 江南大学 Electrodeposition preparation method of light-crosslinking bio-based coating
CN105669972A (en) * 2016-01-27 2016-06-15 吉林大学 Side chain type electroactive polyamide, preparation method and application of side chain type electroactive polyamide in corrosion prevention

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