CN115354331A - Metal corrosion-resistant slow-release microcapsule and preparation method and application thereof - Google Patents
Metal corrosion-resistant slow-release microcapsule and preparation method and application thereof Download PDFInfo
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- CN115354331A CN115354331A CN202211006609.0A CN202211006609A CN115354331A CN 115354331 A CN115354331 A CN 115354331A CN 202211006609 A CN202211006609 A CN 202211006609A CN 115354331 A CN115354331 A CN 115354331A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to the field of metal corrosion prevention, in particular to a metal corrosion prevention slow-release microcapsule and a preparation method and application thereof. The invention provides a metal antiseptic slow-release microcapsule, which comprises an inner core and a coating layer: the coating layer is made of polylactic acid; the material of the inner core comprises gluconate, amino acid and zinc salt. The metal anticorrosion slow-release microcapsule provided by the invention can effectively protect metal materials from corrosion for a long time, maximally protect the power grid grounding metal materials buried in the soil, reduce the operation and maintenance cost and prolong the service life of equipment. Meanwhile, the metal anticorrosion microcapsule can be degraded after the service life is reached, and has no toxic or harmful effect on the nature, especially the buried soil environment.
Description
Technical Field
The invention relates to the field of metal corrosion prevention, in particular to a metal corrosion prevention slow release microcapsule and a preparation method and application thereof.
Background
Grounding is the making of a defined electrical connection between the electrical device and ground. In general applications, a grid system is the most effective grounding system, and therefore, a grid-shaped grounding material network (grounding material for short) is often used for the purpose of effusion in a power generation station and a substation. Since the grounding material is buried in a soil environment in which chemical components and physical properties thereof are intricate for a long time, corrosion of the grounding material in the soil is inevitable. Due to the fact that the ground material is corroded by soil all the year round, the horizontal voltage-sharing conductor of the ground material is corroded, deformed and even broken to different degrees, and the grounding performance is gradually deteriorated. And a fault point with poor electrical connection exists between the ground grid voltage-sharing conductors or between the ground lead and the voltage-sharing conductors. When a fault occurs, if a power system has a ground short circuit fault, the short circuit current cannot be fully diffused in the soil. The local potential difference of the grounding material and the potential of the ground grid are abnormally increased, so that the metal shell of the grounding device has high voltage to endanger the personal safety, besides the safety of operating personnel, the insulation of the secondary device is damaged due to counterattack or cable sheath circulation, the insulation of a secondary protection device is broken down, the high voltage enters a control room, and the accident is enlarged due to misoperation or refusal of monitoring or control equipment. Even damage equipment, enlarge accidents, damage the stability of a power grid system, and bring huge economic loss and adverse social influence. Due to the special use scene of the power grid grounding material, the traditional single anticorrosive coating material is difficult to meet the design requirement.
Because of the advantages of small dosage, investment saving, obvious effect and the like, the corrosion inhibitor becomes the key development direction of the corrosion prevention technology in the field of petroleum transportation and power grids at present. The conventional corrosion inhibitor is divided into an inorganic corrosion inhibitor and an organic corrosion inhibitor, wherein the conventional corrosion inhibitor mainly comprises a corrosion inhibitor composed of metal salts such as a complex acid salt, a tungstate and a molybdate, and the conventional corrosion inhibitor comprises series corrosion inhibitors such as amines, aldehydes, acids and esters, and no matter which corrosion inhibitor has a larger pollution hazard to the natural environment due to the self structure and chemical properties, especially the direct contact of a grounding material of a power grid with soil can cause larger damage to the environment.
Glucose and amino acid are used as indispensable basic units of organic life bodies, are non-toxic and harmless to the environment, have small influence, are more and more concerned by practitioners in recent years, and multiple studies show that glucose or amino acid corrosion inhibitors have an inhibiting effect on the corrosion process of metals. However, metal corrosion is a long-term damage process, and the high-concentration amino acid corrosion inhibitor can protect materials from being damaged by corrosive liquid to the maximum extent in a short time, but in a long term, an effective long-term metal protection mechanism is lacked.
Disclosure of Invention
The invention aims to provide a metal anticorrosion slow-release microcapsule, a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a metal antiseptic slow-release microcapsule, which comprises a core and a coating layer:
the coating layer is made of polylactic acid;
the inner core is made of materials including gluconate, amino acid and zinc salt.
Preferably, the particle size of the metal antiseptic slow-release microcapsule is 0.1-1 μm.
Preferably, the mass ratio of the gluconate to the amino acid to the zinc salt is 1: (0.1-10): (0.1-10).
Preferably, the polylactic acid comprises PLLA and/or PDLA;
the gluconate comprises one or more of calcium gluconate, potassium gluconate, sodium gluconate and zinc gluconate;
the amino acid comprises one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine;
the zinc salt comprises one or more of zinc chloride, zinc sulfate and zinc nitrate.
Preferably, the number of the coating layers is 2 to 10.
Preferably, the cladding layer comprises a PDLA layer and a PLLA layer which are alternately stacked in sequence.
The invention also provides a preparation method of the metal antiseptic slow-release microcapsule, which comprises the following steps:
firstly mixing a template agent and a polylactic acid solution, and coating to obtain polylactic acid microspheres;
secondly, mixing the polylactic acid microspheres and a complexing agent solution for a complexing reaction to obtain hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in a core solution, and filling the core to obtain the metal anticorrosion slow-release microcapsule;
the inner core solution comprises gluconate, amino acid and zinc salt.
Preferably, the concentration of the polylactic acid solution is 1-10 mg/mL;
the polylactic acid solution comprises a PLLA solution or a PDLA solution;
and when the number of the coating layers is 2-10, the first mixing is to sequentially and alternately disperse the template agent in the PLLA solution or the PDLA solution.
Preferably, the complexing agent in the complexing agent solution comprises one or more of ethylenediaminetetraacetic acid, pentasodium ethylenediaminetertramethylenephosphonate, disodium ethylenediaminetetraacetate and sodium iron ethylenediaminetetraacetate.
The invention provides an application of the metal anticorrosion slow-release microcapsule in the technical scheme or the metal anticorrosion slow-release microcapsule prepared by the preparation method in the technical scheme in the anticorrosion of a grounding material of a power grid.
The invention provides a metal antiseptic slow-release microcapsule, which comprises an inner core and a coating layer: the coating layer is made of polylactic acid; the inner core is made of gluconate, amino acid and zinc salt. The metal anticorrosion slow-release microcapsule provided by the invention uses the composite corrosion inhibitor comprising gluconate, amino acid and zinc salt as a core material, and combines the physical characteristic of the microcapsule carrier slow-release corrosion inhibitor, so that the metal material is effectively protected from corrosion for a long time, the power grid grounding metal material embedded in soil can be protected to the maximum extent, the operation and maintenance cost is reduced, and the service life of equipment is prolonged. Meanwhile, the microcapsule with the carrier function uses polylactic acid as a coating layer, can be degraded after the service life is reached, and has no toxic or side effect on the nature, especially the buried soil environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a scanning electron micrograph (B) of the metal antiseptic sustained-release microcapsule of example 1 magnified 2 ten thousand times (A) and magnified 5 ten thousand times;
FIG. 2 is a graph showing a continuous particle size distribution of the metal-preserved controlled-release microcapsule prepared in example 1, wherein the abscissa is the particle diameter and the ordinate is the relative number of particles of different sizes;
FIG. 3 is a graph showing the corrosion of the galvanized iron sheet in soil.
Detailed Description
The invention provides a metal antiseptic slow-release microcapsule, which comprises an inner core and a coating layer:
the coating layer is made of polylactic acid;
the inner core is made of materials including gluconate, amino acid and zinc salt.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, the particle size of the metal antiseptic sustained-release microcapsule is preferably 0.1 to 1 μm, more preferably 0.2 to 0.8 μm, and most preferably 0.2 to 0.6 μm.
In the present invention, the mass ratio of the gluconate to the amino acid to the zinc salt in the mixture of the gluconate, the amino acid and the zinc salt is preferably 1: (0.1-10): (0.1 to 10), more preferably 1: (0.1-5): (0.1 to 5), most preferably 1: (0.1-1): (0.1-1). In the embodiment of the invention, the mass ratio is specifically 1:1:1, zinc gluconate, aspartic acid and zinc sulfate in a mass ratio of 1:1:1, calcium gluconate, glutamic acid and zinc chloride or the mass ratio of 1:0.6:0.4 parts of sodium gluconate, tryptophan and zinc nitrate.
In the present invention, the gluconate preferably comprises one or more of calcium gluconate, potassium gluconate, sodium gluconate and zinc gluconate; when the gluconate is more than two of the specific choices, the proportion of the specific substances is not limited by any special limit, and the specific substances are mixed according to any proportion. In an embodiment of the invention, the gluconate is in particular calcium gluconate, sodium gluconate or zinc gluconate.
In the present invention, the amino acid preferably includes one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine; when the amino acid is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In an embodiment of the invention, the amino acid is in particular aspartic acid, glutamic acid or tryptophan.
In the present invention, the zinc salt preferably includes one or more of zinc chloride, zinc sulfate and zinc nitrate; when the zinc salt is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In an embodiment of the invention, the zinc salt is in particular zinc chloride, zinc sulfate or zinc nitrate.
In the present invention, the coating layer is preferably polylactic acid. The polylactic acid in the present invention is preferably a commercially available product or is preferably prepared using lactide. In the present invention, the method for producing polylactic acid preferably comprises the steps of:
lactide is taken as a monomer to carry out polymerization reaction to obtain a crude product of polylactic acid;
and recrystallizing the crude product of polylactic acid to obtain the polylactic acid.
Lactide is taken as a monomer to carry out polymerization reaction to obtain a crude product of polylactic acid.
The present invention also preferably includes purification of the lactide prior to polymerization. In the present invention, the purification is preferably performed by recrystallization. In the present invention, the recrystallization preferably includes mixing a lactide solution with a catalyst solution, and removing the solvent to obtain lactide. In the present invention, the concentration of the lactide solution is preferably 1 to 10mg/mL, more preferably 2 to 9mg/mL, and most preferably 3 to 8mg/mL; the solvent of the lactide solution preferably comprises one or two of ethyl acetate and toluene; when the solvent is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. In the present invention, the catalyst in the catalyst solution preferably includes one or more of zinc lactate, stannous octoate, and tin tetrachloride; when the catalyst is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion; the solvent in the catalyst solution is preferably toluene; the concentration of the catalyst solution is preferably 0.01 to 0.08g/mL, more preferably 0.02 to 0.06g/mL, and most preferably 0.03 to 0.05g/mL. In the present invention, the mixing is preferably performed in a nitrogen atmosphere; in the present invention, the mixing preferably includes dropping the catalyst solution into the lactide solution; the dripping speed is preferably 20-60drop/min, more preferably 30-50 drop/min, and most preferably 35-45 drop/min; in the present invention, the dropping is preferably performed using a constant pressure dropping funnel. After the mixing is complete, the present invention also preferably includes removing the solvent; the process for removing the solvent is not particularly limited, and may be performed by a process known to those skilled in the art. In the present invention, the process of removing the solvent is preferably performed in a rotary evaporator.
In the present invention. The temperature of the polymerization reaction is preferably 100 to 200 ℃, more preferably 120 to 190 ℃, and most preferably 140 to 170 ℃; the time is preferably 2 to 12 hours, more preferably 4 to 10 hours, and most preferably 6 to 8 hours; the polymerization reaction is preferably carried out in a vacuum vessel, preferably a heatable vacuum oven or an evacuable glass vessel.
After the crude product of polylactic acid is obtained, the crude product of polylactic acid is recrystallized to obtain the polylactic acid. In the present invention, the recrystallization preferably comprises dissolving the polylactic acid in a good solvent, and then adding the solution to a poor solvent to precipitate; the good solvent is preferably dichloromethane and/or trichloromethane; when the good solvent is dichloromethane and trichloromethane, the invention has no special limitation on the proportion of the dichloromethane and the trichloromethane, and the good solvent can be mixed according to any proportion. In the present invention, the poor solvent is preferably petroleum ether and/or diethyl ether; when the poor solvent is petroleum ether and diethyl ether, the mixture ratio of the petroleum ether and the diethyl ether is not limited in any particular way, and the petroleum ether and the diethyl ether can be mixed according to any mixture ratio. The present invention does not have any particular limitation on the recrystallization conditions, and the recrystallization can be carried out by a procedure well known to those skilled in the art.
In the present invention, the polylactic acid preferably comprises PLLA and/or PDLA; the PLLA is preferably a commercially available product or prepared from L-lactide; the PDLA is preferably a commercially available product or is prepared using D-lactide.
In the present invention, the number of coating layers is preferably 2 to 10, more preferably 3 to 9, and most preferably 4 to 8. In the present invention, the coating layer preferably includes a PDLA layer and a PLLA layer alternately stacked in this order. In the present invention, the PLLA is preferably a commercially available product, or is prepared using L-lactide; the PDLA is preferably a commercially available product or is prepared using D-lactide.
The metal anticorrosion slow-release microcapsule provided by the invention uses the composite corrosion inhibitor comprising gluconate, amino acid and zinc salt as a core material, and combines the physical characteristic of the microcapsule carrier slow-release corrosion inhibitor, so that the metal material is effectively protected from corrosion for a long time, the power grid grounding metal material embedded in soil can be protected to the maximum extent, the operation and maintenance cost is reduced, and the service life of equipment is prolonged. Meanwhile, the microcapsule with the carrier function uses polylactic acid as a coating layer, can be degraded after the service life is reached, and has no toxic or side effect on the nature, especially the buried soil environment.
The invention provides a preparation method of a metal antiseptic slow-release microcapsule, which comprises the following steps:
firstly mixing a template agent and a polylactic acid solution, and coating to obtain polylactic acid microspheres;
secondly, mixing the polylactic acid microspheres and a complexing agent solution for a complexing reaction to obtain hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in a core solution, and filling the core to obtain the metal anticorrosion slow-release microcapsule;
the inner core solution comprises gluconate, amino acid and zinc salt.
According to the invention, a template agent and a polylactic acid solution are firstly mixed and coated to obtain the polylactic acid microspheres.
In the present invention, the particle size of the template is preferably 0.1 to 1 μm, more preferably 0.2 to 0.8. Mu.m, and most preferably 0.2 to 0.6. Mu.m. In the present invention, the template agent preferably includes one or more of calcium carbonate, magnesium carbonate, barium carbonate, and calcium lignosulfonate, and more preferably includes one or more of calcium carbonate, magnesium carbonate, and barium carbonate; when the template agent is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. The source of the template agent is not limited in any way in the present invention, and products well known to those skilled in the art can be used. When the template agent is calcium carbonate, the calcium carbonate is preferably a commercially available product or synthesized by reaction; the reaction synthesis is preferably prepared by carrying out precipitation reaction on carbonate and calcium salt; the carbonate is preferably one or more of calcium carbonate, potassium carbonate, magnesium carbonate and sodium carbonate; when the carbonate is more than two of the specific choices, the specific proportion of the specific substances is not limited in any way, and the specific substances are mixed according to any proportion; the calcium salt is preferably one or more of calcium chloride, calcium sulfate, calcium carbonate and calcium nitrate; when the calcium salts are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
In the present invention, the concentration of the polylactic acid solution is preferably 1 to 10mg/mL, more preferably 2 to 9mg/mL, and most preferably 3 to 8mg/mL; the solvent of the polylactic acid solution preferably comprises one or more of acetonitrile, dichloromethane and chloroform; when the solvent is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. In an embodiment of the invention, the solvent is in particular acetonitrile. In the present invention, the polylactic acid solution preferably includes a PLLA solution or a PDLA solution. In the present invention, the mass ratio of the templating agent to the polylactic acid is preferably 1:5 to 40, more preferably 1:10 to 30, most preferably 1:15 to 20.
In the present invention, the first mixing is preferably performed under stirring. In the present invention, the temperature of the stirring is preferably 20 to 60 ℃, more preferably 25 to 50 ℃, and most preferably 30 to 40 ℃; the time is preferably 20 to 60min, more preferably 25 to 50min, and most preferably 30 to 40min. The stirring speed is not limited in any way, and the stirring can be carried out by adopting a process well known to a person skilled in the art.
In the present invention, the first mixing is preferably performed 2 to 10 times, more preferably 3 to 9 times, and most preferably 4 to 8 times. In the present invention, when the first mixing is performed 2 to 10 times, the first mixing is preferably performed such that the template is alternately dispersed in the PLLA solution or the PDLA solution in sequence.
In the present invention, it is also preferable to include centrifugation and washing in this order after the completion of the stirring. The conditions for the centrifugation are not particularly limited in the present invention, and the centrifugation may be carried out by a method known to those skilled in the art. In the present invention, the washing agent used for the washing preferably includes one or more of acetonitrile, dichloromethane, and chloroform; when more than two of the specific choices are adopted for the washing, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the examples of the present invention, the washing agent used for the washing is specifically acetonitrile. The washing conditions of the present invention are not particularly limited, and the washing may be carried out by a method known to those skilled in the art.
In the invention, the first mixing has the effects that the template agent is uniformly dispersed in the polylactic acid solution and is coated on the surface of the template agent, and the polylactic acid solution can coat the originally rough template layer by layer, so that the surface is smooth and the wall thickness is controllable. In the invention, when the first mixing is carried out for 2-10 times, the stereotactic action between the PDLA and the PLLA can generate a self-assembly driving force, and the self-assembly driving force can be carried out layer by layer on the surface of the template agent and tightly combined to form a smooth and compact polylactic acid coating layer.
After the polylactic acid microspheres are obtained, the polylactic acid microspheres and the complexing agent solution are mixed for the second time to carry out a complexing reaction, so that the hollow polylactic acid microspheres are obtained.
In the present invention, the concentration of the complexing agent solution is preferably 0.01 to 1mol/L, more preferably 0.1 to 1mol/L, and most preferably 0.1 to 0.5mol/L. In the invention, the complexing agent in the complexing agent solution comprises one or more of ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid pentasodium salt, ethylenediaminetetraacetic acid disodium salt and ethylenediaminetetraacetic acid ferric sodium salt, and preferably comprises one or more of ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid pentasodium salt and ethylenediaminetetraacetic acid disodium salt; when the complexing agents are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the substances can be mixed according to any proportion. In the embodiment of the invention, the complexing agent is specifically ethylenediamine tetraacetic acid, ethylenediamine tetramethylene phosphonic acid pentasodium or ethylenediamine tetraacetic acid disodium.
In the present invention, the second mixing means is preferably vortex oscillation. In the invention, the rotation speed of the vortex oscillation is preferably 800-2000 r/min, more preferably 1000-1800 r/min, and most preferably 1200-1600 r/min; the time is preferably 10 to 24 hours, more preferably 12 to 20 hours, and most preferably 14 to 18 hours.
In the present invention, in the second mixing process, the complexing agent and the metal ions in the template agent undergo a complexing reaction to generate a water-soluble complex, thereby decomposing and removing the template agent.
After the hollow polylactic acid microspheres are obtained, the hollow polylactic acid microspheres are soaked in a core solution for core filling, and the metal anticorrosion sustained-release microcapsules are obtained.
In the present invention, the solute in the core solution preferably includes gluconate, amino acid and zinc salt. The concentration of the gluconate of the core solution is preferably 5-20 g/L, more preferably 8-18 g/L, and most preferably 10-15 g/L; the concentration of the amino acid is 5 to 20g/L, more preferably 8 to 18g/L, and most preferably 10 to 15g/L; the concentration of the zinc salt is 5 to 20g/L, more preferably 8 to 18g/L, and most preferably 10 to 15g/L.
In the present invention, the gluconate preferably comprises one or more of calcium gluconate, potassium gluconate, sodium gluconate and zinc gluconate; when the gluconate is more than two of the specific choices, the proportion of the specific substances is not limited by any special limit, and the specific substances are mixed according to any proportion. In an embodiment of the present invention, the gluconate is specifically calcium gluconate, sodium gluconate or zinc gluconate.
In the present invention, the amino acid preferably includes one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine; when the amino acid is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In an embodiment of the invention, the amino acid is in particular aspartic acid, aspartic acid or tryptophan.
In the present invention, the zinc salt preferably includes one or more of zinc chloride, zinc sulfate and zinc nitrate; when the zinc salt is more than two of the above specific choices, the present invention does not have any special limitation on the proportion of the above specific substances, and the specific substances can be mixed according to any proportion. In an embodiment of the invention, the zinc salt is in particular zinc chloride, zinc sulfate or zinc nitrate.
In the present invention, the solvent of the core solution is preferably water.
In the present invention, the soaking is preferably performed under the condition of vortex oscillation. In the invention, the rotating speed of the rotary oscillation is preferably 800-2000 r/min, more preferably 1000-1800 r/min, and most preferably 1200-1600 r/min; the time is preferably 10 to 48 hours, more preferably 15 to 40 hours, most preferably 20 to 30 hours.
In the present invention, it is also preferable to include washing and drying sequentially after the vortex oscillation is completed. In the present invention, the detergent used for washing is preferably deionized water. The washing process of the present invention is not particularly limited, and may be carried out by a process known to those skilled in the art. In the invention, the drying mode is drying; in the invention, the drying temperature is preferably 100-200 ℃, more preferably 120-180 ℃, and most preferably 150-170 ℃; the time is preferably 12 to 24 hours, more preferably 14 to 20 hours, most preferably 16 to 18 hours. In the present invention, the drying is preferably performed using an oven.
In the invention, the inner core solution is diffused into the hollow polylactic acid microspheres through concentration difference, the inner core solution on the surface is removed through washing, and the solvent is removed through drying, so that the metal anticorrosion slow-release microcapsule is finally obtained.
The invention provides an application of the metal anticorrosion slow-release microcapsule in anticorrosion of a power grid grounding material.
For further illustration of the present invention, the metal-preserved sustained-release microcapsule provided by the present invention, its preparation method and application are described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 300mg of L-lactide in toluene to prepare 100mL of L-lactide solution;
dissolving 0.3g of stannous octoate in toluene to prepare 10mL of catalyst solution;
and (3) dripping the stannous octoate solution into the L-lactide solution at the speed of 30drop/min by adjusting a constant-pressure dropping funnel in the nitrogen atmosphere, uniformly stirring, and removing the solvent by using a rotary evaporator to obtain the L-lactide.
Placing the purified L-lactide in a heatable vacuum oven, wherein the heating temperature is 120 ℃, and the heating time is 12 hours, so as to obtain a crude product of polylactic acid;
the crude polylactic acid was dissolved in 100mL of chloroform, and then precipitated with 200mL of diethyl ether to give PLLA.
Dissolving 300mg of D-lactide in toluene to prepare 100mL of D-lactide solution;
dissolving 0.3g of stannous octoate in toluene to prepare 10mL of catalyst solution;
and (3) dripping the stannous octoate solution into the D-lactide solution at the speed of 30drop/min by adjusting a constant-pressure dropping funnel in the nitrogen atmosphere, uniformly stirring, and removing the solvent by using a rotary evaporator to obtain the D-lactide.
Placing the purified D-lactide in a heatable vacuum oven, and heating at 120 ℃ for 12 hours to obtain a crude product of polylactic acid;
the crude polylactic acid was dissolved in 100mL of chloroform, and then precipitated with 200mL of diethyl ether to obtain PDLA.
Dissolving 500mg PLLA in acetonitrile to obtain 100mL PLLA solution;
dissolving 500mg of PDLA in acetonitrile to obtain 100mL of PDLA solution;
dispersing 100mg of calcium carbonate in a PLLA solution, stirring for 30 minutes at 30 ℃, centrifuging and washing with acetonitrile to prepare polylactic acid microspheres, dispersing the polylactic acid microspheres in a PDLA solution by the same method, and alternately coating to finally prepare the polylactic acid microspheres with 4 layers of coatings;
dispersing the polylactic acid microspheres in 0.1mol/L ethylene diamine tetraacetic acid solution, and performing vortex oscillation for 12 hours at the rotating speed of 1500r/min to remove inorganic calcium carbonate templates, thereby obtaining hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in 200mL of core solution, wherein the core solution contains 1.6g of aspartic acid, 1.6g of zinc sulfate and 1.6g of zinc gluconate, and the solvent is water; and (3) carrying out vortex oscillation for 24h at the rotating speed of 1500r/min, washing, placing in an oven at 50 ℃, and drying for 24h to obtain the metal antiseptic slow-release microcapsule. The scanning electron microscope picture of the metal antiseptic slow-release microcapsule is shown in figure 1 and figure 2.
As can be seen from figure 1, the metal antiseptic slow-release microcapsule has a complete structure, a smooth and compact surface and a particle size distribution of 0.1-1 μm. As can be seen from figure 2, the average particle size of the metal antiseptic slow-release microcapsule is about 300nm.
Example 2
Dissolving 500mg of PLLA in acetonitrile to obtain 100mL of PLLA solution;
dissolving 500mg of PDLA in acetonitrile to obtain 100mL of PDLA solution;
50mg of calcium carbonate is dispersed in the PLLA solution, stirred for 30 minutes at 50 ℃, centrifuged by acetonitrile and washed to prepare the polylactic acid microspheres. Dispersing the polylactic acid microspheres in a PDLA solution by the same method, and alternately coating to finally prepare 6-layer coated polylactic acid microspheres;
dispersing the polylactic acid microspheres in 0.2mol/L disodium ethylene diamine tetraacetate solution, and performing vortex oscillation for 10 hours at the rotating speed of 1000r/min to remove the inorganic calcium carbonate template to obtain hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in 200mL of core solution, wherein the core solution contains 2g of glutamic acid, 2g of zinc chloride and 2g of calcium gluconate, and the solvent is water; and (3) performing vortex oscillation for 24h at the rotating speed of 1000r/min, washing, placing in a 50 ℃ oven, and drying for 16h to obtain the metal anticorrosion slow-release microcapsule.
Example 3
Dissolving 800mg of PLLA in acetonitrile to obtain 200mL of PLLA solution;
dissolving 800mg of PDLA in acetonitrile to obtain 200mL of PDLA solution;
160mg of calcium carbonate is dispersed in the PLLA solution, stirred for 30 minutes at 50 ℃, centrifuged by acetonitrile and washed to prepare the polylactic acid microspheres. Dispersing the polylactic acid microspheres in a PDLA solution by the same method, and alternately coating to finally prepare 10-layer coated polylactic acid microspheres;
dispersing the polylactic acid microspheres in 0.1mol/L ethylene diamine tetraacetic acid pentasodium salt solution, and removing the inorganic calcium carbonate template by vortex oscillation for 24 hours at the rotation speed of 1800r/min to obtain hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in 500mL of core solution, wherein the core solution contains 8g of tryptophan, 8g of zinc nitrate and 8g of sodium gluconate, and the solvent is water; and (3) performing vortex oscillation for 24h at the rotating speed of 1800r/min, washing, placing in a 50 ℃ oven, and drying for 18h to obtain the metal anticorrosion slow-release microcapsule.
Test example
Selecting natural environment soil with uniform soil texture and without impurities such as massive stone particles, obvious plant root systems and the like. The soil was set in the following two groups: keeping the original physical and chemical properties of the soil unchanged, adding 5wt% of the metal corrosion-resistant slow-release microcapsule prepared in the embodiment 3 into the soil, mixing the metal corrosion-resistant slow-release microcapsule and the soil, and rotating a roller at the rotating speed of 60r/min for 30min to fully and uniformly mix the metal corrosion-resistant slow-release microcapsule and the soil to form a group A; untreated soil was set as group B. And selecting galvanized iron sheets as corroded metals to be respectively placed in the two groups of soils for performance characterization. To accelerate the corrosion, a cross-recess was scribed in the center of the metal sheet to a depth of about 300 μm. The results are shown in FIG. 3. Wherein (A) and (A ') are respectively corrosion condition graphs when galvanized iron sheets in natural soil are buried for 1 week and 6 months, and (B) and (B') are respectively corrosion condition graphs when galvanized iron sheets in soil added with 5wt% of metal corrosion-prevention slow-release microcapsules are buried for 1 week and 6 months.
As can be seen from fig. 3, the corrosion of the galvanized iron sheets in natural soil is severe after the galvanized iron sheets are filled in the soil for six months, while the galvanized iron sheets are not significantly corroded in the soil to which the metal corrosion-prevention slow-release microcapsules are added. Therefore, the invention can prevent metal corrosion for a long time and has wide application prospect.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The metal corrosion-resistant slow-release microcapsule is characterized by comprising an inner core and a coating layer:
the coating layer is made of polylactic acid;
the inner core is made of materials including gluconate, amino acid and zinc salt.
2. The microcapsule according to claim 1, wherein the microcapsule has a particle size of 0.1-1 μm.
3. The metal antiseptic slow-release microcapsule according to claim 1 or 2, wherein the mass ratio of the gluconate to the amino acid to the zinc salt is 1: (0.1-10): (0.1-10).
4. The metal-preserved slow release microcapsule according to claim 3, wherein the polylactic acid comprises PLLA and/or PDLA;
the gluconate comprises one or more of calcium gluconate, potassium gluconate, sodium gluconate and zinc gluconate;
the amino acid comprises one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine;
the zinc salt comprises one or more of zinc chloride, zinc sulfate and zinc nitrate.
5. The metal-antiseptic slow-release microcapsule according to claim 4, wherein the number of the coating layers is 2-10.
6. The metal-antiseptic slow-release microcapsule according to claim 5, wherein the coating layer comprises a PDLA layer and a PLLA layer which are alternately stacked in sequence.
7. A process for preparing a metal-preserved slow-release microcapsule according to any one of claims 1 to 6, comprising the steps of:
firstly mixing a template agent and a polylactic acid solution, and coating to obtain polylactic acid microspheres;
secondly, mixing the polylactic acid microspheres and a complexing agent solution for a complexing reaction to obtain hollow polylactic acid microspheres;
soaking the hollow polylactic acid microspheres in a core solution, and filling the core to obtain the metal anticorrosion slow-release microcapsule;
the inner core solution comprises gluconate, amino acid and zinc salt.
8. The method according to claim 7, wherein the concentration of the polylactic acid solution is 1 to 10mg/mL;
the polylactic acid solution comprises a PLLA solution or a PDLA solution;
and when the number of the coating layers is 2-10, the first mixing is to alternately disperse the template agent in the PLLA solution or the PDLA solution in sequence.
9. The method of claim 7, wherein the complexing agent in the complexing agent solution comprises one or more of ethylenediaminetetraacetic acid, pentasodium ethylenediaminetetramethylenephosphonate, disodium ethylenediaminetetraacetate, and sodium iron ethylenediaminetetraacetate.
10. The use of the metal corrosion-prevention slow-release microcapsule according to any one of claims 1 to 6 or the metal corrosion-prevention slow-release microcapsule prepared by the preparation method according to any one of claims 7 to 9 in the corrosion prevention of grounding materials of power grids.
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