CN102327862A - Polymer composite coating technology capable of reducing corrosion rates of magnesium-based material and magnesium-based material device - Google Patents

Polymer composite coating technology capable of reducing corrosion rates of magnesium-based material and magnesium-based material device Download PDF

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CN102327862A
CN102327862A CN201110193356A CN201110193356A CN102327862A CN 102327862 A CN102327862 A CN 102327862A CN 201110193356 A CN201110193356 A CN 201110193356A CN 201110193356 A CN201110193356 A CN 201110193356A CN 102327862 A CN102327862 A CN 102327862A
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based material
coating
magnesium
composite coating
polymer composite
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CN102327862B (en
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黄楠
王娟
赵元聪
陈佳龙
万国江
王进
郭丽莎
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Guangzhou Nanchuang Everest Medical Technology Co Ltd
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CHENGDU JIAODA MAIDIKE TECHNOLOGY Co Ltd
Southwest Jiaotong University
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Abstract

The invention discloses a polymer composite coating technology capable of reducing corrosion rates of a magnesium-based material and a magnesium-based material device. The technology comprises the following steps of: coating a surface corrosion type polymer coating on the magnesium-based material and the surface of the magnesium-based material device; and coating a functionalized active layer on the surface corrosion type polymer coating. By the coating, the corrosion rates of the magnesium-based material and the magnesium-based material device can be effectively reduced, and the requirements of the magnesium-based material and the magnesium-based material device in an operating and using environment can be met.

Description

A kind of polymer composite coating technology that reduces mg-based material and device corrosion rate thereof
Technical field
The present invention relates to functional material, especially mg-based material surface corrosion-resistant treatments technical field.
Background technology
Magnesium alloy is a kind of very desirable modern industry structural material, is widely used in aerospace industry in early days, in fields such as traffic, optical instrument, electronics industries great development has been arranged also at present.Recently, magnesium and alloy thereof have obtained showing great attention to of biomaterial circle.Generally pay attention to and problem anxious to be solved but the too fast corrosion rate of mg-based material and device thereof remains, this also is that people once abandoned the main cause that magnesium is used in medicine equipment embedded material field.
With the intravascular stent is example, because the diastole of blood vessel is shunk, the long-term non-degradable support of implanting might cause the infringement of endarterium layer, causes the vascular smooth muscle hyper-proliferative, causes ISR.Therefore, people begin to pay close attention to the high-fall support of separating, and magnesium and alloy thereof become one of timbering material the most likely.But the magnesium base support of prior art for preparing is general owing to degraded, and in one month, just loses enabling capabilities soon.So the surface modification to mg-based material and device thereof is one of present more effective means to improve its decay resistance.For example Medtronic Vascular Inc. discloses the controlled degradation of magnesium bracket at Chinese patent 200980114738.8, and this patent utilization body degradation polymer and bioactivator carry out surface modification to magnesium bracket.
The present invention proposes the corrosion rate that a kind of new method can effectively reduce mg-based material and device thereof, to satisfy its demand in use.Can be applied to magnesium base intravascular stent, magnesium base bone anchor tool (screws, bone clamping plate), stapler etc.For ease of clear narration, mg-based material and all be called mg-based material below the device.
Summary of the invention
Seeing that the deficiency of the existing program of above statement; The present invention aims to provide a kind of polymer composite coating technology that reduces the corrosion rate of mg-based material and device thereof; The polymer composite coating of this coating technology preparation can effectively slow down mg-based material and device corrosion rate thereof; Particularly under the situation of coating and matrix material plastic deformation, coating still can play the better protect effect to base material.
The object of the invention is realized through following means.
A kind of method that obtains the polymer composite coating of reduction corrosion rate on the mg-based material surface, adopt following steps to reduce the polymer composite coating of corrosion rate in the mg-based material surface-coated:
(1) be that the erodible polymer organic solution of 0.05%-2% is coated in clean substrate surface with mass fraction; And carry out dried;
(2) device after (1) is handled is immersed in the solution that contains the functionalization active material 1-24 hour; The auto polymerization of functionalization active material is deposited on the erodible polymeric layer of base material, takes out dry back and on its erosion type polymer-coated layer, obtain the functionalization active material layer;
(3) repeat (2) step once more than, obtain the purpose product.
Adopt method of the present invention; With the coating that mg-based material and device thereof directly contact is surface erosion type polymer; Its degradation behavior surface erosion type degraded is promptly degraded to inside by material surface gradually, and whole degradation process is a linear process; The degradation rate linearity is controlled, and is the zero order kinetics degraded.This is different from the polymer coating material that prior art adopts body degraded mode; The molecular weight of body degradation-type polymer coating polymer in corrosion process continues to descend; The polymer mechanical property sharply descends; Being easy to be corroded penetrates the exposure matrix, often just loses the protection effect during one's term of military service at device, causes magnesium base corrosion rate too fast.And the degraded mode of surface erosion type polymer coating is to begin from the surface gradually to inside, and its molecular weight remains unchanged, and can before itself degraded fully, well protect the substrate mg-based material always, stops solution or medium and the direct haptoreaction of substrate; And the catabolite of polymer is nearly neutral carbon dioxide and water, has fundamentally avoided the magnesium base accelerated corrosion that causes because of degraded, and in use also can be owing to local acid too highly not impact environment for use.Be the acid defective that then can cause subacute stent thrombosis in vivo like magnesium base intravascular stent as if the superficial degradation product; Use surface erosion type polymer coating magnesium base intravascular stent can effectively improve the corrosion resistance of intravascular stent, make intravascular stent the performance support function the time significant prolongation and improve clinical serviceability.
Above-mentioned surface erosion type polymer is: Merlon, cholic acid ring-opening polymerisation PLA, gather one or more the blend in acid anhydrides, the poe.Above polymer is the good surface erosion type polymer of widely used degradability.Simultaneously these several base polymers have good plastic deformation ability, under the service condition that mg-based material and device thereof need be out of shape, still can play good effect to slowing down the substrate corrosion rate.
The functionalization active layer that combines even compact on the surface of surface erosion type polymer; Can further slow down the degraded of surface erosion type polymer; And then the corrosion rate of slowing down mg-based material and device thereof realized duplicate protection, to satisfy the demand of device application.Simultaneously this type functionalization active layer only needs with the mode auto polymerization of soaking at polymer surfaces, and its preparation process is simple to operation, also need not expensive dedicated equipment, and preparation cost is low.In addition, this layer function active layer has not only been made contribution aspect corrosion-resistant, also makes to scribble the mg-based material of polymer and the surface active of device goes out more active group, helps further realizing surface grafting biomolecule or functional high-polymer.
The specific embodiment
Below in conjunction with embodiment enforcement of the present invention is done further to describe, it is pure that the embodiment agents useful for same is analysis.
Embodiment 1, corrosion-resistant finishes are the mg-based material and the preparation of devices thereof of Merlon-dobutamine coating, the steps include:
A, Merlon added in the chloroform organic solvent to form mass fraction be 2% solution;
B, utilize the ultrasonic atomizatio spraying method, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 24 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the Merlon coating, be placed in the cushioning liquid of Tris of dobutamine and soaked 24 hours, dopamine concentration is 20mg/mL, temperature is 20 ℃.Repetitive operation 2 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply Merlon-dobutamine polymer coating.Embodiment 2
Corrosion-resistant finishes is the mg-based material and the preparation of devices thereof of PTMC-dopamine coating, the steps include:
A, PTMC added in the carrene organic solvent to form mass fraction be 0.1% solution;
The method of solvent evaporates film forming is soaked in B, utilization, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 48 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the PTMC coating, be placed in the weakly alkaline solution of Tris of dopamine and soaked 24 hours, dopamine concentration is 2mg/mL, PH=8.5, temperature is 20 ℃.Repetitive operation 2 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply PTMC-dopamine coating.
Embodiment 3
Corrosion-resistant finishes is the mg-based material and the preparation of devices thereof of gathering acid anhydrides-DOPA coating, the steps include:
A, will gather acid anhydrides and add that to form mass fraction in the isopropyl alcohol organic solvent be 0.25% solution;
B, utilize pulling film forming method, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 48 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, C step is had mg-based material and the device thereof that gathers the acid anhydrides coating, be placed in the weakly alkaline solution of Tris of DOPA and soaked 24 hours, DOPA concentration is 10mg/mL, PH=8.5, and temperature is 20 ℃.Repetitive operation 10 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply and gather acid anhydrides-DOPA coating.
Embodiment 4
Corrosion-resistant finishes is the mg-based material and the preparation of devices thereof of poe-ethylenediamine gallamide coating, the steps include:
A, poe is added carrene, and to form mass fraction be 0.5% solution;
B, utilize pulling film forming method, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 24 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the poe coating, be placed in the cushioning liquid of Tris of ethylenediamine gallamide and soaked 12 hours, ethylenediamine gallamide concentration is 2mg/mL, temperature is 20 ℃.Repetitive operation 20 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply poe-ethylenediamine gallamide coating.
Embodiment 5
Corrosion-resistant finishes is a cholic acid ring-opening polymerisation PLA-3,4, and the mg-based material and the preparation of devices thereof of 5-trihydroxy-1-benzene methanamine coating the steps include:
A, cholic acid ring-opening polymerisation PLA is added carrene, and to form mass fraction be 1.5% solution;
The method of film forming is soaked in B, utilization, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 24 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the poe coating, be placed on 3,4, soaked 6 hours in the cushioning liquid of the Tris of 5-trihydroxy-1-benzene methanamine, 3,4,5-trihydroxy-1-benzene methanamine concentration is 20 ℃ for the 5mg/mL temperature.Repetitive operation 10 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply cholic acid ring-opening polymerisation PLA-3,4,5-trihydroxy-1-benzene methanamine coating.
Embodiment 6
Corrosion-resistant finishes is the mg-based material and the preparation of devices thereof of Merlon/poe blend-2-(3.4.5-trihydroxy phenyl) ethamine coating, the steps include:
A, 55 mass parts Merlon and 45 mass parts poes are added oxolane, and to form mass fraction be 1% solution;
B, utilize the ultrasonic atomizatio spraying method, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 24 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the poe coating, be placed in the cushioning liquid of Tris of hexamethylene diamine gallamide and soaked 12 hours, hexamethylene diamine gallamide concentration is 1mg/mL, temperature is 20 ℃.Repetitive operation 5 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply Merlon/poe blend-2-(3.4.5-trihydroxy phenyl) ethamine coating.
Embodiment 7
Corrosion-resistant finishes is Merlon/cholic acid ring-opening polymerisation PLA/poe blend-3, and the mg-based material and the preparation of devices thereof of 4-dihydroxy benzenes amine 8th lunar month coating the steps include:
A, with 30 mass parts Merlon, 25 mass parts cholic acid ring-opening polymerisation PLAs and 45 mass parts poes add oxolane to form mass fraction are 0.2% solution;
B, utilize the pulling film forming method, on the solution coating of magnesium sill and device thereof with the A step; The specific practice that mg-based material and device thereof clean is: mg-based material and device thereof placed the acetone soln sonic oscillation 3 minutes, and sonic oscillation 3 minutes in ethanol solution takes out then again, dries up.
C, B is gone on foot coating mg-based material and device thereof be placed in the vacuum drying chamber after the drying, promptly get.
It is 24 hours drying times that coating mg-based material and device thereof are placed on concrete parameter dry in the vacuum drying chamber, and temperature is 20 ℃.
D, with mg-based material and device thereof that C step has the poe coating, be placed on 3, soaked 24 hours in the cushioning liquid of the Tris of the 4-dihydroxy benzenes amine 8th lunar month, 3,4-dihydroxy benzenes amine 8th lunar month concentration is 2mg/mL, temperature is 20 ℃.Repetitive operation 2 times.
E, be placed in the vacuum drying chamber after the drying, promptly get with C step coating mg-based material and device thereof.
Like this, promptly made a kind of mg-based material and device thereof with corrosion-resistant finishes, this mg-based material and device surface thereof apply Merlon/cholic acid ring-opening polymerisation PLA/poe blend-3,4-dihydroxy benzenes amine 8th lunar month coating.

Claims (6)

1. the polymer composite coating that can reduce mg-based material and device corrosion rate thereof is technological, adopts following steps to reduce the polymer composite coating of corrosion rate in the mg-based material surface-coated:
(1) be that the erosion type polymer organic solution of 0.05%-2% is coated in clean substrate surface with mass fraction; And carry out dried;
(2) device after (1) is handled is immersed in the solution that contains the functionalization active material 1-24 hour; The auto polymerization of functionalization active material is deposited on the erosion type polymeric layer of base material, takes out dry back and on its erosion type polymer-coated layer, obtain the functionalization active material layer;
(3) repeat (2) step once more than, obtain the purpose product.
2. a kind of polymer composite coating technology that reduce mg-based material and device corrosion rate thereof according to claim 1; It is characterized in that said erosion type polymer is at least a in the following material: Merlon, cholic acid ring-opening polymerisation PLA, gather acid anhydrides, poe.
3. a kind of polymer composite coating technology that reduce mg-based material and device corrosion rate thereof according to claim 1; It is characterized in that; Said functionalization active material is one of following material: catechol amino-compound, pyrogallol class amino-compound.
4. a kind of polymer composite coating technology that reduce mg-based material and device corrosion rate thereof according to claim 3 is characterized in that said catechol amino-compound is DOPA, dopamine and derivative thereof.
5. a kind of polymer composite coating technology that reduce mg-based material and device corrosion rate thereof according to claim 3; It is characterized in that; Said pyrogallol class amino-compound is ethylenediamine gallamide, 2-(3.4.5-trihydroxy phenyl) ethamine, 3; 4,5-trihydroxy-1-benzene methanamine, 3, the 4-dihydroxy benzenes amine 8th lunar month.
6. a kind of polymer composite coating technology that reduce mg-based material and device corrosion rate thereof according to claim 1; It is characterized in that said coated polymer coating operation comprises: utilize ultrasonic atomizatio spraying method or dipping pulling film forming method or soak solvent evaporates to become embrane method.
CN201110193356.8A 2011-07-12 2011-07-12 Polymer composite coating technology capable of reducing corrosion rates of magnesium-based material and magnesium-based material device Active CN102327862B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698322A (en) * 2012-05-14 2012-10-03 西南交通大学 Preparation method of biomedical materials of multiclass functional group rich in amino group, carboxyl group and benzoquinonyl group
CN104195535A (en) * 2014-08-12 2014-12-10 西南交通大学 Modification method for improving corrosion resistance and surface functionalization of biomedical magnesium-based metal material
CN111059999A (en) * 2019-12-31 2020-04-24 苏州能斯达电子科技有限公司 Flexible bending sensor and manufacturing method thereof
WO2023053059A1 (en) * 2021-09-30 2023-04-06 Universidade Do Porto Antifouling compound, method and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090240323A1 (en) * 2008-03-20 2009-09-24 Medtronic Vascular, Inc. Controlled Degradation of Magnesium Stents
CN101703428A (en) * 2009-10-28 2010-05-12 西南交通大学 Intravascular scaffold provided with anti-restenosis coating layer and preparation method thereof
CN102000658A (en) * 2010-12-15 2011-04-06 西南交通大学 Polydopamine-based biofunction modification method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090240323A1 (en) * 2008-03-20 2009-09-24 Medtronic Vascular, Inc. Controlled Degradation of Magnesium Stents
CN101703428A (en) * 2009-10-28 2010-05-12 西南交通大学 Intravascular scaffold provided with anti-restenosis coating layer and preparation method thereof
CN102000658A (en) * 2010-12-15 2011-04-06 西南交通大学 Polydopamine-based biofunction modification method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698322A (en) * 2012-05-14 2012-10-03 西南交通大学 Preparation method of biomedical materials of multiclass functional group rich in amino group, carboxyl group and benzoquinonyl group
CN102698322B (en) * 2012-05-14 2014-11-26 西南交通大学 Preparation method of biomedical materials of multiclass functional group rich in amino group, carboxyl group and benzoquinonyl group
CN104195535A (en) * 2014-08-12 2014-12-10 西南交通大学 Modification method for improving corrosion resistance and surface functionalization of biomedical magnesium-based metal material
CN111059999A (en) * 2019-12-31 2020-04-24 苏州能斯达电子科技有限公司 Flexible bending sensor and manufacturing method thereof
WO2023053059A1 (en) * 2021-09-30 2023-04-06 Universidade Do Porto Antifouling compound, method and uses thereof

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