CN108619565A - A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof - Google Patents

A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof Download PDF

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CN108619565A
CN108619565A CN201810400485.1A CN201810400485A CN108619565A CN 108619565 A CN108619565 A CN 108619565A CN 201810400485 A CN201810400485 A CN 201810400485A CN 108619565 A CN108619565 A CN 108619565A
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magnesia
composite coating
lactic acid
preparation
present
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陈民芳
梁慧
李枭
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Tianjin University of Technology
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Tianjin University of Technology
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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Abstract

The present invention relates to organic/inorganic composite material technical fields, provide a kind of preparation method of l-lactic acid/magnesia composite coating, include the following steps：In matrix surface home position polymerization reaction is occurred into for levorotatory lactide, magnesia, organic coupling agent and obtains l-lactic acid/magnesia composite coating；The home position polymerization reaction carries out under conditions of organic solvent and catalyst；It can be in one step fabricated in situ l-lactic acid of Mg alloy surface/magnesia composite coating using preparation method provided by the invention, the composite coating 15 days percent weight loss in simulating liquid are less than 6%, composite coating does not continue to weightlessness substantially within 15~30 days, and resistance to corrosion is significantly improved.

Description

A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof
Technical field
The present invention relates to organic/inorganic composite material technical field, more particularly to a kind of l-lactic acid/magnesia is compound The preparation method of coating and application.
Background technology
Magnesium and its magnesium alloy have good biocompatibility, biological degradability and mechanical compatibility, are ideal biologies It is implanted into material, is ideal bone fracture internal fixation material.But since its high velocity erosion rate in human body leads to implant devices very It fails soon because of corrosion, and when corrosion rate is too fast will produce drastically increasing for local pH change dramatically and amounts of hydrogen, make human body It can not bear, limit the development of magnesium and its alloy as implantation material, therefore the biodegradation for controlling magnesium and magnesium alloy makes it It is particularly critical to meet Clinical practice requirement.
In controlling the biodegradable technology of magnesium alloy, organic coating has due to its simple and cheap technical process Good application prospect.It, must be nontoxic and with good biofacies as biological magnesium and its protective coating of magnesium alloy Capacitive.L-lactic acid has recyclability, in people's degradable in vivo, and has good biocompatibility, is that current commercialization can The preferred material of degradation bone implanting part, has been used clinically for the reparation of non-bearing bone.High molecular weight l-lactic acid (PLLA) because of its enough initial strength, good biocompatibility and degradability, but main problem existing for pure polylactic acid It is：1) it is implanted into Preliminary degradation speed and loss of strength is too fast, and because autocatalytic effect keeps degradation process uncontrollable；2) degradation is intermediate Body lactic acid reduces body fluid pH value strongly, makes implant ambient enviroment in apparent acid.
For MgO whiskers because having special pattern, the influence to material property is much larger than common MgO particles.MgO whiskers are maximum The characteristics of be that there is very high intensity, therefore be well suited as reinforcing or the supporting material of various composite materials, be a kind of excellent Composite material reinforcement body, but its enhancing composite material corrosion resistance in terms of research it is very few.
Zhao grows profit et al. and prepares PLGA coatings in Mg alloy surface using dip-coating czochralski method, but can only effective protection magnesium alloy Corrosion degradation does not occur at implantation initial stage, there is no solve corrosivity of the implantation later stage acidic environment to magnesium alloy coating.Lu is flat Et al. PLLA sealing pores are carried out to magnesium alloy differential arc oxidation film, one side MAO/PLLA sealing of hole composite membranes effectively improve film layer Corrosion resistance makes the effective support blood vessels of holder prevent restenosis, on the other hand since the degradation of MAO/PLLA films makes differential arc oxidation The micropore of film surface accelerates the degradation of magnesium alloy, and magnesium alloy is made to be degraded quickly suction after completing the narrow task of support blood vessels It receives, but the resistance to corrosion of pure PLLA is weaker compared to PLLA/MgO, even if the film layer resistance to corrosion with MAO after compound It still cannot be satisfied requirement of the magnesium alloy coating for corrosion resistance.Although at this stage it is proposed that using czochralski method in magnesium Alloy surface prepares PLLA/MgO composite coatings, but this coating technology is prepared using the method that PLLA is blended with MgO, Technique is cumbersome, can not effectively improve the resistance to corrosion of coating.
Invention content
The object of the present invention is to provide a kind of preparation method of l-lactic acid/magnesia composite coating, the present invention The preparation method of offer is simple for process, and obtained l-lactic acid/magnesia composite coating has higher resistance to corrosion.
The present invention provides a kind of preparation methods of l-lactic acid/magnesia composite coating, include the following steps：
Levorotatory lactide, magnesia and organic coupling agent are subjected to home position polymerization reaction in matrix surface, obtained left-handed poly- Lactic acid/magnesia composite coating；
It is carried out under the conditions of the home position polymerization reaction is existing for organic solvent and catalyst.
Preferably, the mass ratio of the levorotatory lactide, magnesia, organic coupling agent and catalyst is 50~100:1~ 5:0.5~6:1~5.
Preferably, the levorotatory lactide quality and the volume ratio of organic solvent are 1~1.5g：1~10ml.
Preferably, the organic coupling agent includes oleic acid and/or 3- glycidol butyldimethylsilyl coupling agents.
Preferably, the organic solvent includes chloroform and/or dichloromethane.
Preferably, the reaction temperature of the home position polymerization reaction is 80~140 DEG C, and the reaction time is 24~48h.
Preferably, the catalyst is stannous octoate.
A kind of l-lactic acid being prepared the present invention provides above-mentioned technical proposal/magnesia composite coating, including Magnesia and l-lactic acid, the magnesia are connected with l-lactic acid in the form of chemical bond.
The present invention also provides a kind of l-lactic acid/magnesia composite coating magnesium alloy, including magnesium alloy and it is coated on The l-lactic acid of magnesium alloy matrix surface/magnesia composite coating, the l-lactic acid/magnesia composite coating are above-mentioned Composite coating described in technical solution or the composite coating prepared using above-mentioned preparation method.
The present invention also provides l-lactic acid described in above-mentioned technical proposal/magnesia composite coating magnesium alloys to prepare bone Fixed material, porous bone repair material, Dental implantion material, dental prosthetic material and angiocarpy bracket material biological implantation material In application.
The present invention provides a kind of preparation methods of l-lactic acid/magnesia composite coating, include the following steps：It will be left In matrix surface home position polymerization reaction occurs for rotation lactide, magnesia, organic coupling agent, and to obtain l-lactic acid/magnesia compound Coating；The home position polymerization reaction carries out under conditions of organic solvent and catalyst；Preparation method provided by the invention By adding organic coupling agent, magnesia is allow directly to be prepared with lactide open loop in situ bonding under the effect of the catalyst It is bad to avoid unmodified MgO and PLLA compatibilities without being modified to MgO for l-lactic acid/magnesia composite coating The problem of, the binding performance of the two is improved, the resistance to corrosion of coating is enhanced；The present invention utilizes MgO in physiological environment simultaneously The Mg of middle corrosion release2+Ion neutralizes l-lactic acid degradation acidity, inhibits autocatalytic effect, material is implanted by improvement Surrounding enviroment, indirect enhance the resistance to corrosion of composite coating.The experimental results showed that：Preparation method provided by the invention can With in one step fabricated in situ l-lactic acid of Mg alloy surface/magnesia composite coating, and the l-lactic acid/oxidation prepared 15 days percent weight loss of magnesium composite coating composite coating in simulating liquid are less than 6%, and 15~30 days composite coatings are substantially not It is further continued for weightlessness, corrosion rate is effectively reduced.
Description of the drawings
Fig. 1 is the SEM figures of magnesium-based l-lactic acid/magnesia composite coating in the embodiment of the present invention 1；
Fig. 2 is the SEM figures of magnesium-based l-lactic acid/magnesia composite coating in the embodiment of the present invention 2；
Fig. 3 is the SEM figures of magnesium-based l-lactic acid/magnesia composite coating in the embodiment of the present invention 3；
Fig. 4 is the SEM figures of magnesium-based l-lactic acid/magnesia composite coating in the embodiment of the present invention 4；
Fig. 5 is the shape appearance figure that surface coats l-lactic acid/magnesia composite coating magnesium alloy in the embodiment of the present invention 1；
Fig. 6 is that the magnesium-based composite coating of the different magnesia crystal whisker additive amounts of the embodiment of the present invention 1~3 loses in simulated body fluid Weight change curve；
Fig. 7 be the different magnesia crystal whisker additive amounts of the embodiment of the present invention 1~3 magnesium-based composite coating in simulated body fluid pH It is worth change curve.
Specific implementation mode
The present invention provides a kind of preparation methods of l-lactic acid/magnesia composite coating, include the following steps：
Levorotatory lactide, magnesia and organic coupling agent are subjected to home position polymerization reaction in matrix surface, obtained left-handed poly- Lactic acid/magnesia composite coating；It is carried out under the conditions of the home position polymerization reaction is existing for organic solvent and catalyst.
Levorotatory lactide, magnesia, organic coupling agent, catalyst and organic solvent are preferably mixed to get reaction by the present invention Liquid.
In the present invention, the mass ratio of the levorotatory lactide, magnesia, organic coupling agent and catalyst be preferably 50~ 100:1~5:0.5~6：1~5, more preferably 80~100：1~3：1~3：1~3, most preferably 100：1：1：1 or 100：1： 3：3.
In the present invention, the quality of the levorotatory lactide and the volume ratio of organic solvent are preferably 50~100g：1~ 10ml, more preferably 80~100g：5~10ml, most preferably 100g：10ml.
In the present invention, the levorotatory lactide chemical formula is L-3,6- dimethyl -2,5- diketone-Isosorbide-5-Nitrae-dioxa hexamethylenes Alkane；The cost of material requested can be greatly lowered using levorotatory lactide as raw material by the present invention, expand its application range.
In the present invention, the magnesia is preferably magnesia crystal whisker or nano oxidized magnesium granules；
In the present invention, the grain size of the nano oxidized magnesium granules is preferably 120~180nm, more preferably 150nm； In the present invention, the external degradation behavior of the nano oxidized magnesium granules energy Effective Regulation polylactic acid neutralizes l-lactic acid degradation The acid intermediate product of generation, improves the hydrophily of polylactic acid, accelerates Preliminary degradation rate, but with the extension of degradation time, Nano oxidized magnesium granules can effectively inhibit the autocatalysis that polylactic acid is degraded.
In the present invention, the preparation method of the nano oxidized magnesium granules preferably includes：
1) by MgC12Aqueous solution and (COOH)2·2H2O is mixed to get suspension at a temperature of 30~50 DEG C；
2) intermediate product MgC is dried to obtain after being filtered, washed the suspension2O4·nH2O；
3) by the intermediate product in 500~700 DEG C of 3~7h of roasting temperature, cooling obtains nano oxidized magnesium granules.
In the present invention, the MgC12(COOH)2·2H2The ratio between amount of substance of O is preferably 2：1；The MgC12Water The concentration of solution is preferably 1~2mol/L, more preferably 1.5mol/L.In the present invention, the MgC12Aqueous solution and (COOH)2·2H2O order by merging is preferably by (COOH)2·2H2MgC1 is added in O2In aqueous solution；The present invention is for above-mentioned raw materials Source there is no particular/special requirement, using commercial goods and experiment raw material.
In the present invention, the mixing preferably carries out under stirring conditions, and time of the stirring is preferably 10~ 20min；The stirring preferably includes magnetic agitation or mechanical agitation.
The present invention is not particularly limited the mode being filtered, washed and dried, and selects the filtering of this field routine, washes It washs and dry technology scheme.In the present invention, the drying carries out preferably in vacuum drying chamber, the temperature of the drying Preferably 70~90 DEG C, more preferably 80 DEG C；The time of the drying is preferably 1~3h, more preferably 2h.
In the present invention, the magnesia crystal whisker is white powder, the grain size of the magnesia crystal whisker is preferably 120~ 180nm, more preferably 150nm.In the present invention, it is produced when the addition of magnesia crystal whisker can reduce l-lactic acid biodegradation Raw acidity so that l-lactic acid Preliminary degradation is too fast to be mitigated, and is realized magnesia crystal whisker and is corroded to l-lactic acid The regulation and control of rate, are effectively protected magnesium alloy, improve the resistance to corrosion of magnesium-based composite coating；And magnesia crystal whisker drops The Mg discharged when solution2+Ion is intracellular cation, and human body daily demand amout may participate in protein synthesis up to 300~400mg, A variety of enzymes, the activity of adjusting neuromuscular and central nervous system stimulate the activity of osteoblast, animal body interplantation in vivo for activation Enter the magnesium alloy composite coating material post-etching rate well below the painting that the magnesium alloy and coating of non-coating are pure organic matter Layer material.
The present invention does not have the preparation method of the magnesia crystal whisker special restriction, using known to those skilled in the art Prepared by technical solution, in the present invention, the preparation of the magnesia crystal whisker preferably includes following steps：
1) by MgCl2Aqueous solution and NaCO3It is aged after aqueous solution mixing, obtains magnesia crystal whisker presoma；
2) the magnesia crystal whisker presoma is calcined to 1~5h at 700~800 DEG C, obtains magnesia crystal whisker.
The present invention is preferably by MgCl2Aqueous solution and NaCO3It is aged after aqueous solution mixing, obtains magnesia crystal whisker presoma.
In the present invention, the MgCl2Aqueous solution and NaCO3The volume ratio of aqueous solution is preferably 1：1；The MgCl2It is water-soluble The concentration of liquid is preferably 0.5~1mol/L, more preferably 0.6mol/L；The NaCO3The concentration of aqueous solution is preferably 0.5~ 1mol/L, more preferably 0.6mol/L.
In the present invention, the MgCl2Aqueous solution and NaCO3The mixing of aqueous solution preferably carries out under stirring conditions.This Invention does not have particular/special requirement to the rate of the stirring, and the time of the stirring is preferably 10~20min；The preferred packet of stirring Include magnetic agitation or mechanical agitation.
In the present invention, the ageing preferably carries out at room temperature, and the time of the ageing is preferably 5~15h, more preferably For 10h.
The present invention is preferably filtered, washs and dries to the product after the ageing after aging successively, is aoxidized Magnesium whisker presoma.Magnesia crystal whisker presoma in the present invention is MgCO3·3H2O。
The present invention is not particularly limited the mode being filtered, washed and dried, and selects the filtering of this field routine, washes It washs and dry technology scheme.In the present invention, the temperature of the drying is preferably 60~100 DEG C, more preferably 80 DEG C；Institute It is preferably 1~5h to state the dry time, more preferably 4h.
After obtaining magnesia crystal whisker presoma, the magnesia crystal whisker presoma is calcined 1 at 700~800 DEG C by the present invention ~5h, obtains magnesia crystal whisker.
The present invention preferably before calcination tiles magnesia crystal whisker presoma uniformly, to improve calcining effect.In the present invention In, the calcining carries out preferably in crucible, and the heating rate when calcining is preferably 1~5 DEG C/min.
In the present invention, the temperature of the calcining is preferably 720~780 DEG C, more preferably 750 DEG C.
After calcining, the present invention preferably cools down the product after the calcining, obtains magnesia crystal whisker.
In the present invention, the organic coupling agent preferably includes oleic acid and/or 3- glycidol butyldimethylsilyl coupling agents. In the present invention, when the organic coupling agent is oleic acid, the dosage of the organic coupling agent is preferably levorotatory lactide quality 1%~6%；When the organic coupling agent is 3- glycidol butyldimethylsilyl coupling agents, the use of the organic coupling agent Amount is preferably the 0.5%~3% of levorotatory lactide quality.
In the present invention, the catalyst is preferably stannous octoate.The present invention uses stannous octoate for catalyst, Neng Gou The open loop home position polymerization reaction of matrix surface catalyzing levorotatory lactide and magnesia crystal whisker, without changing to magnesia crystal whisker Property, avoid unmodified magnesia crystal whisker and the bad problem of l-lactic acid compatibility.
In the present invention, the organic solvent preferably includes chloroform and/or dichloromethane.
In the present invention, the mixing of the levorotatory lactide, magnesia, organic coupling agent, catalyst and organic solvent is excellent It is selected under the conditions of ultrasonic vibration and carries out, the time of the ultrasonic vibration is preferably 10~30min, more preferably 20min.The present invention There is no particular/special requirement for the order by merging of levorotatory lactide, magnesia, organic coupling agent, catalyst and organic solvent, to appoint Order of anticipating mixes.
After obtaining reaction solution, preferably in matrix surface home position polymerization reaction is occurred for reaction solution by the present invention, is dried to obtain a left side Revolve polylactic acid/magnesia composite coating.
In the present invention, the temperature of the home position polymerization reaction is preferably 80~140 DEG C, more preferably 100~120 DEG C； The time of the home position polymerization reaction is preferably 24~48h, more preferably 30~40h.In the present invention, the in-situ polymerization is anti- It should preferably be carried out under oil bath counterflow condition.
In the present invention, described matrix can be arbitrary metal material.In an embodiment of the present invention, described matrix is preferred For magnesium alloy substrate；The diameter of the magnesium alloy is preferably 8mm, and thickness is preferably 3mm；The element composition of the magnesium alloy is preferred For Mg-3Zn-0.8Zr-0.3Ca-0.3Ag.The present invention does not have particular/special requirement for the source of magnesium alloy, using it is well known that Prepare alloy technical solution prepare.
In the present invention, the drying is preferably dried in vacuo, and the present invention is for the vacuum drying pressure without spy It is different to limit；In the present invention, the drying temperature is preferably 50~60 DEG C, and drying time is preferably 4~6h.
A kind of l-lactic acid being prepared the present invention also provides above-mentioned technical proposal/magnesia composite coating, packet Magnesia and l-lactic acid are included, the magnesia is connected with l-lactic acid in the form of chemical bond；In the present invention, described The mass percentage of magnesia is preferably 1~3%；The number-average molecular weight of the l-lactic acid is preferably 20~300,000, more Preferably 250,000.
The present invention also provides a kind of l-lactic acid/magnesia composite coating magnesium alloy, including magnesium alloy and it is coated on The l-lactic acid of magnesium alloy matrix surface/magnesia composite coating, the l-lactic acid/magnesia composite coating are above-mentioned Coating described in technical solution or the coating prepared using preparation method described in above-mentioned technical proposal.
In the present invention, the preparation of the l-lactic acid/magnesia composite coating magnesium alloy is preferably using magnesium alloy as base Body prepares the l-lactic acid/magnesia composite coating, herein according to above-mentioned technical proposal in magnesium alloy matrix surface It repeats no more.
The present invention also provides l-lactic acid described in above-mentioned technical proposal/magnesia composite coating magnesium alloys to prepare bone Fixed material, porous bone repair material, Dental implantion material, dental prosthetic material and angiocarpy bracket material biological implantation material In application, the present invention is not particularly limited the application process of l-lactic acid/magnesia composite coating magnesium alloy, selects This field routine.
In order to further illustrate the present invention, brilliant to l-lactic acid provided by the invention/magnesia with reference to embodiment Palpus composite coating and its preparation method and application is described in detail, but they cannot be interpreted as to the scope of the present invention Restriction.
Embodiment 1
1) preparation of magnesia crystal whisker
Compound concentration is the MgCl of 0.6mol/L2·6H2O and Na2CO3Each 50ml of aqueous solution, measured with graduated cylinder 20mlNaCO3Aqueous solution is slowly dropped to the MgCl in magnetic agitation state of same volume2·6H2In O aqueous solutions, stirring 20min obtains suspension；Suspension is aged 10h at room temperature, is filtered, washing, 80 DEG C of dry 4h obtain magnesia crystal whisker Presoma MgCO3·3H2O.The presoma MgCO that will be obtained3·3H2O is put into crucible, is uniformly paved, 750 DEG C of calcining 4h, control 5 DEG C/min of heating rate processed, is slowly cooled to room temperature to obtain white powder magnesia crystal whisker.
2) preparation of magnesium alloy substrates
Raw material is high purity magnesium (99.99wt%), and high purity zinc (99.99wt%), Mg-30%Zr alloys, Mg-30%Ca are closed Gold, Mg-10%Ag alloys, design alloy Mg-3Zn-0.8Zr-0.3Ca-0.3Ag.Alloy uses vaccum sensitive stove, and in argon The cylinder ingot casting of diameter 60mm is cast under gas shielded after melting.Then, the 420 DEG C of homogenizing cast ingots 13 of metal that will be obtained A hour simultaneously removes surface scale through mechanical treatment.The ingot casting of obtained surface-brightening is subjected to hot extrusion, technique uses Forward extrusion, it is 300 DEG C to squeeze temperature, final to squeeze the bar for being diameter 8mm, then with wire cutting machine cutting thickness is the small of 3mm Disk.It is dry after being cleaned by ultrasonic wash with distilled water and in absolute ethyl alcohol.
3) preparation of magnesium-based l-lactic acid/magnesia composite coating
Levorotatory lactide 1.5g, MgO whisker 0.015g, 3- glycidol butyldimethylsilyl coupling agent is weighed respectively 0.0075g, stannous octoate 0.045g and 10ml chloroform be added to sonic oscillation in the single necked round bottom flask of 100ml 10min；By absolute ethyl alcohol processing and it is dried be put into round-bottomed flask for 8mm × 3mm magnesium alloy disks, then round bottom is burnt Bottle is placed in oil bath pan, 140 DEG C of back flow reaction 36h；After reaction, cooling, magnesium alloy composite coating is taken out, is being dried in vacuo 60 DEG C of vacuum drying 6h, obtain magnesium-based l-lactic acid/magnesia composite coating in case, magnesia crystal whisker in the composite coating Content is 1wt%.
In situ bonding reaction, shape can occur with magnesia crystal whisker for l-lactic acid in the present embodiment as seen from Figure 1 At the coating of compact structure.
Embodiment 2
1) MgO whiskers prepare it is same as Example 1；
2) magnesium alloy prepares same as Example 1；
3) preparation of magnesium-based l-lactic acid/magnesia composite coating
Weigh respectively levorotatory lactide 1.5g, MgO whisker 0.03g, 3- glycidol butyldimethylsilyl coupling agent 0.045g, The chloroform of stannous octoate 0.015g and 10ml are added to sonic oscillation 10min in the single necked round bottom flask of 100ml；It will be anhydrous Alcohol treatment and it is dried be put into round-bottomed flask for 8mm × 3mm magnesium alloy substrates, round-bottomed flask is then placed oil bath pan In, 140 DEG C of back flow reaction 36h；After reaction, cooling, take out magnesium alloy composite coating, 60 DEG C of vacuum in vacuum drying chamber Dry 6h obtains magnesium-based l-lactic acid/magnesia composite coating, and magnesia crystal whisker content is 2wt% in the composite coating.
In situ bonding reaction, shape can occur with magnesia crystal whisker for l-lactic acid in the present embodiment as seen from Figure 2 At the coating of compact structure.
Embodiment 3：
1) MgO whiskers prepare it is same as Example 1；
2) magnesium alloy is prepared same as Example 1,
3) prepared by Mg alloy surface composite coating material
Levorotatory lactide 1.5g, MgO whisker 0.045g, oleic acid 0.015g, stannous octoate 0.045g and 10ml are weighed respectively Chloroform be added to sonic oscillation 20min in the single necked round bottom flask of 100ml；By absolute ethyl alcohol processing and dried it is 8mm × 3mm magnesium alloy materials are put into round-bottomed flask, then round-bottomed flask are placed in oil bath pan, 140 DEG C of back flow reaction 36h； After reaction, cooling, magnesium alloy materials are taken out, 60 DEG C of vacuum drying 6h, obtain the left-handed poly- breast of magnesium-based in vacuum drying chamber Acid/magnesia composite coating, magnesia crystal whisker content is 3wt% in the composite coating.
In situ bonding reaction, shape can occur with magnesia crystal whisker for l-lactic acid in the present embodiment as seen from Figure 3 At the coating of compact structure.
Embodiment 4：
1) MgO whiskers prepare it is same as Example 1；
2) magnesium alloy is prepared same as Example 1,
3) prepared by Mg alloy surface composite coating material
Levorotatory lactide 1.5g, MgO whisker 0.015g, oleic acid 0.09g, stannous octoate 0.075g and 5ml are weighed respectively Dichloromethane is added to sonic oscillation 10min in the single necked round bottom flask of 100ml；By absolute ethyl alcohol processing and dried it is 8mm × 3mm magnesium alloy materials are put into round-bottomed flask, then round-bottomed flask are placed in oil bath pan, 80 DEG C of back flow reaction 48h； After reaction, cooling, magnesium alloy materials are taken out, 60 DEG C of vacuum drying 6h, obtain the left-handed poly- breast of magnesium-based in vacuum drying chamber Acid/magnesia composite coating, magnesia crystal whisker content is 1wt% in the composite coating.
In situ bonding reaction, shape can occur with magnesia crystal whisker for l-lactic acid in the present embodiment as seen from Figure 4 At the coating of compact structure.
Embodiment 5
Attached Figures 5 and 6 are that l-lactic acid/magnesia composite coating combination magnesium that the embodiment of the present invention 1~3 is prepared closes Application test of the golden material in simulated body fluid：
The small pieces that laboratory sample is cut into 1cm*1cm are put into nut bottle, and 10ml simulated body fluids, 37 DEG C of water-baths are added Concussion needs two days one to change since simulated body fluid is perishable, and the PH of leaching liquor after impregnating is measured with pH acidometers, and time of measuring is The the 1st, 3,5,7,15,31 day after immersion, liquid is changed before degradation for 24 hours, measurement result is degradation rate interior for 24 hours.Measure sample simultaneously The weight of product, passes through formulaCalculate weightlessness (m0For sample original quality, mdTo impregnate the matter of rear film Amount), and calculate its error.It is 3 to impregnate parallel sample quantity used.
It can be seen that by weightless change curve of the magnesium-based coating material in attached drawing 5 in simulating liquid：It is carried using the present invention Magnesium-based l-lactic acid/magnesia composite coating that the preparation method of confession obtains, 15 days of composite coating are lost in simulating liquid Weight percentage is less than 6%, and composite coating does not continue to weightlessness substantially within 15~30 days, and corrosion rate is effectively reduced, and is improved The resistance to corrosion of composite coating.
By magnesium-based coating material in Fig. 6, pH value curve can be seen that in simulating liquid：Utilize system provided by the invention Magnesium-based l-lactic acid/magnesia composite coating that Preparation Method obtains, the pH value in simulating liquid as time increases and It improves, can effectively neutralize the acidity generated in polylactic acid degradation process, it is compound to enhance by the pH value for improving ambient enviroment The resistance to corrosion of coating.
And when MgO whisker additive amounts are 1wt%, the degradation of magnesia crystal whisker has just neutralized polylactic acid degradation and has generated Acidity, and magnesia crystal whisker improves the crystal property of PLLA, therefore the degradation rate of polylactic acid slows down, and additive amount increases To 2wt%, solution alkaline after seven days, accelerates the degradation of PLLA after 3wt%.Illustrate that magnesia crystal whisker additive amount is 1wt% When composite material degradation rate slow down so that PLLA Preliminary degradations are too fast to be mitigated, realize magnesia crystal whisker content choosing Select the regulation and control to PLLA corrosion rates.
Embodiment 6
1) preparation of magnesium oxide nanoparticle
Compound concentration is the MgCl of 1.5mol/L2Aqueous solution, 40 DEG C of magnetic agitations make it fully dissolve；By (COOH)2· 2H2O is added to the MgCl in magnetic agitation220min (MgC1 are reacted in aqueous solution2(COOH)2·2H2The ratio between amount of substance of O It is 2:1) suspension of White Flocculus generation, is obtained；Suspension is filtered, is done in 80 DEG C of vacuum drying chambers after washing Dry 1h obtains intermediate product MgC2O4·nH2O；Intermediate product is roasted into 4h at 600 DEG C, control heating rate is 5 DEG C/min, cold But nano oxidized magnesium granules are obtained to room temperature, the particle size of the nano oxidized magnesium granules is in 150nm or so.
2) preparation of magnesium alloy substrates
Raw material is high purity magnesium (99.99wt%), and high purity zinc (99.99wt%), Mg-30%Zr alloys, Mg-30%Ca are closed Gold, Mg-10%Ag alloys, design alloy Mg-3Zn-0.8Zr-0.3Ca-0.3Ag.Alloy uses vaccum sensitive stove, and in argon The cylinder ingot casting of diameter 60mm is cast under gas shielded after melting.Then, the 420 DEG C of homogenizing cast ingots 13 of metal that will be obtained A hour simultaneously removes surface scale through mechanical treatment.The ingot casting of obtained surface-brightening is subjected to hot extrusion, technique uses Forward extrusion, it is 300 DEG C to squeeze temperature, final to squeeze the bar for being diameter 8mm, then with wire cutting machine cutting thickness is the small of 3mm Disk.It is dry after being cleaned by ultrasonic wash with distilled water and in absolute ethyl alcohol.
3) preparation of magnesium-based l-lactic acid/magnesia composite coating
Levorotatory lactide 1.5g, the coupling of nano oxidized magnesium granules 0.015g, 3- glycidol butyldimethylsilyl are weighed respectively Agent 0.0075g, stannous octoate 0.045g and 10ml chloroform be added to sonic oscillation in the single necked round bottom flask of 100ml 10min；By absolute ethyl alcohol processing and it is dried be put into round-bottomed flask for 8mm × 3mm magnesium alloy disks, then round bottom is burnt Bottle is placed in oil bath pan, 140 DEG C of back flow reaction 36h；After reaction, cooling, magnesium alloy composite coating is taken out, is being dried in vacuo 60 DEG C of vacuum drying 6h, obtain magnesium-based l-lactic acid/magnesia composite coating in case, nano magnesia in the composite coating The content of particle is 1wt%.

Claims (10)

1. a kind of preparation method of l-lactic acid/magnesia composite coating, includes the following steps：
By levorotatory lactide, magnesia and organic coupling agent matrix surface carry out home position polymerization reaction, obtain l-lactic acid/ Magnesia composite coating；
It is carried out under the conditions of the home position polymerization reaction is existing for organic solvent and catalyst.
2. preparation method according to claim 1, which is characterized in that the levorotatory lactide, magnesia, organic coupling agent Mass ratio with catalyst is 50~100:1~5:0.5~6:1~5.
3. preparation method according to claim 1, which is characterized in that the body of the levorotatory lactide quality and organic solvent Product is than being 1~1.5g：1~10ml.
4. preparation method according to claim 1 or 2, which is characterized in that the organic coupling agent includes oleic acid and/or 3- Glycidol butyldimethylsilyl coupling agent.
5. preparation method according to claim 1 or 3, which is characterized in that the organic solvent include chloroform and/or Dichloromethane.
6. preparation method according to claim 1, which is characterized in that the reaction temperature of the home position polymerization reaction be 80~ 140 DEG C, the reaction time is 24~48h.
7. preparation method according to claim 1 or 2, which is characterized in that the catalyst is stannous octoate.
8. the l-lactic acid that preparation method described in claim 1~7 any one obtains/magnesia composite coating, including oxygen Change magnesium and l-lactic acid, the magnesia are connected with l-lactic acid in the form of chemical bond.
9. a kind of l-lactic acid/magnesia composite coating magnesium alloy, which is characterized in that including magnesium alloy and be coated on magnesium alloy The l-lactic acid of matrix surface/magnesia composite coating, the l-lactic acid/magnesia composite coating are claim 8 The composite coating or the composite coating prepared using any one of claim 1~7 the method.
10. l-lactic acid described in claim 9/magnesia composite coating magnesium alloy prepare bone immobilizing material, porous bone is repaiied Application in multiple material, Dental implantion material, dental prosthetic material and angiocarpy bracket material biological implantation material.
CN201810400485.1A 2018-04-28 2018-04-28 A kind of l-lactic acid/magnesia composite coating and the preparation method and application thereof Pending CN108619565A (en)

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CN117045872A (en) * 2023-10-13 2023-11-14 四川大学 Corrosion-resistant composite coating, magnesium-based bracket containing corrosion-resistant composite coating and preparation method of magnesium-based bracket

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Publication number Priority date Publication date Assignee Title
CN111068106A (en) * 2019-11-27 2020-04-28 东南大学 Medical degradable antibacterial composite material and preparation method and application thereof
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CN117045872A (en) * 2023-10-13 2023-11-14 四川大学 Corrosion-resistant composite coating, magnesium-based bracket containing corrosion-resistant composite coating and preparation method of magnesium-based bracket
CN117045872B (en) * 2023-10-13 2023-12-15 四川大学 Corrosion-resistant composite coating, magnesium-based bracket containing corrosion-resistant composite coating and preparation method of magnesium-based bracket

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