CN112225836B - A kind of metal ion transfer carrier and its preparation method and application - Google Patents
A kind of metal ion transfer carrier and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种金属离子转移载体及其制备方法和应用，涉及金属离子应用领域。金属离子转移载体为混合溶液，混合溶液包括基材和金属离子，基材与金属离子通过配位作用结合，基材为含有羧基的水溶性化合物，混合溶液中基材与金属离子的摩尔比为30‑200:5‑30。通过调节基材(含有羧基的水溶性化合物)与金属离子的用量比例，使得水溶性化合物的部分羧基与金属离子通过配位作用结合，水溶性化合物的另一部分羧基以游离的形式存在于溶液中从而保持金属离子转移载体在较宽的pH范围内的水溶性。因此，本发明提供的金属离子转移载体不会发生中性或碱性条件下金属离子的沉淀或分布不均匀的现象。
The invention discloses a metal ion transfer carrier, a preparation method and application thereof, and relates to the application field of metal ions. The metal ion transfer carrier is a mixed solution, the mixed solution includes a base material and a metal ion, the base material and the metal ion are combined through coordination, the base material is a water-soluble compound containing a carboxyl group, and the molar ratio of the base material to the metal ion in the mixed solution is 30‑200:5‑30. By adjusting the dosage ratio of the base material (water-soluble compound containing carboxyl group) to the metal ion, part of the carboxyl group of the water-soluble compound is combined with the metal ion through coordination, and another part of the carboxyl group of the water-soluble compound exists in the solution in a free form Thus, the water solubility of the metal ion transfer carrier is maintained in a wide pH range. Therefore, the metal ion transfer carrier provided by the present invention will not cause precipitation or uneven distribution of metal ions under neutral or alkaline conditions.
Description
Technical Field
The invention relates to the field of metal ion application, in particular to a metal ion transfer carrier and a preparation method and application thereof.
Background
The high molecular film forming material is a composite material which forms a layer of film with certain adhesive strength and mechanical strength on the surface of an article by coating, spraying and the like so as to protect the article or endow the surface of the article with multiple functions, and generally comprises a film forming agent, a coloring agent, an auxiliary agent, a medium and the like. Therefore, polymeric film-forming materials have been widely used in manufacturing industries, such as leather coating materials, furniture coating materials, rubber coating materials, and the like.
Since most single-component polymeric film-forming materials exhibit poor mechanical properties or single functions, it is common to combine multiple polymeric film-forming materials in practical applications.
A common method for improving the mechanical property, corrosion resistance, antibacterial property and the like of a high-molecular film-forming material is to mix a nano material to modify a film-forming material matrix. Numerous reports have shown that nanoparticles (e.g., SiO)2，ZnO，TiO2Nanoparticles in the form of Ag, etc.) incorporated into a matrix of the film-forming material may enhance one or more properties of the film. The nano particles have the problem of high dispersion difficulty in a film-forming material matrix.
Metal ions are widely used as cross-linking agents in many material structures to improve the mechanical properties, flame retardancy, antibacterial properties, etc. of materials by utilizing the coordination binding ability of the metal ions to compounds containing coordination groups (such as substances containing carboxyl, amino, phenolic hydroxyl, etc.). Due to the poor alkali resistance of metal ions, the currently used method is to add metal ions to the material in an environment with a pH of 2 to 5. However, this method has a large pH limitation and is not suitable for neutral or alkaline materials.
Currently, polymeric film-forming materials (e.g., aqueous coating materials) typically have a pH of 6 to 9, and most metal ions precipitate at this pH and are difficult to distribute uniformly throughout the material.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a metal ion transfer carrier, a preparation method thereof and application thereof to solve the technical problems.
The invention is realized by the following steps:
a metal ion transfer carrier is a mixed solution, the mixed solution comprises a base material and metal ions, the base material and the metal ions are combined through coordination, the base material is a water-soluble compound containing carboxyl, and the molar ratio of the base material to the metal ions in the mixed solution is 30-200: 5-30.
The inventors have creatively provided a metal ion transfer carrier which maintains water solubility of the metal ion transfer carrier over a wide pH range by adjusting the amount ratio of a substrate (a water-soluble compound having carboxyl groups) to metal ions so that a part of the carboxyl groups of the water-soluble compound are bound to the metal ions by coordination and another part of the carboxyl groups of the water-soluble compound are present in a solution in a free form. The metal ion transfer carrier can be directly used for adding metal ions of a high-molecular film-forming material, and can meet the water solubility in a wide pH range due to free carboxyl, so that the metal ion transfer carrier can not precipitate or distribute uniformly metal ions under neutral or alkaline conditions.
Through a large number of experiments, the inventors have verified that if metal ions are directly added into a high-molecular film-forming material (polyacrylate emulsion), the metal ions introduced into the high-molecular film-forming material are rapidly precipitated and cannot be uniformly distributed.
In a preferred embodiment of the present invention, the pH of the metal ion transfer carrier is 2 to 11.
In a preferred embodiment of the present invention, the pH of the metal ion transfer carrier is 6 to 9.
In a preferred embodiment of the present invention, the pH of the metal ion transfer carrier is 7 to 8.
The metal ion transfer carrier provided by the invention can be applied to a high-molecular film-forming material with a wider pH range.
In a preferred embodiment of the present invention, the water-soluble compound containing a carboxyl group includes one or more of polyacrylic acid polymer, polyacrylate polymer, citric acid, tartaric acid, carboxymethyl cellulose and carboxymethyl cellulose salt.
Preferably, the polyacrylic acid has a weight average molecular weight of 1000-125000 g/mol.
The citric acid is anhydrous citric acid, and preferably, the carboxymethyl cellulose (CMC) may be sodium carboxymethyl cellulose.
In a preferred embodiment of the present invention, the metal ion is a divalent metal ion, a trivalent metal ion, a tetravalent metal ion, or a higher valence metal ion with more than four valences;
preferably, the divalent metal ion is selected from Zn2+、Cu2+、Co2+Or Ni2+；
The trivalent metal ion is selected from Al3+、Fe3+Or Cr3+；
The tetravalent metal ion is selected from Sn4+、Ge4+、Ti4+、Zr4+。
The high valence metal ion may be Mn ion or the like.
A preparation method of a metal ion transfer carrier comprises the following steps:
mixing the base material and metal ions according to a molar ratio of 30-200: 5-30.
The preparation method provided by the invention is simple, has low preparation cost, and can realize industrial production and application.
At the above molar ratio, it is ensured that the substrate has a sufficient amount of carboxyl groups to coordinate all metal ions, while the substrate and the remaining part of the carboxyl groups remain water-soluble.
In a preferred embodiment of the present invention, the preparation method further comprises: and adjusting the pH value of the metal ion transfer carrier after the base material and the metal ions are mixed to 2-11, and keeping the metal ion transfer carrier in a clear state. Preferably, the pH is 6-9; preferably, the pH is 7-8.
In a preferred embodiment of the present invention, the preparation method further comprises: after the pH value is adjusted, the metal ion transfer carrier is concentrated;
preferably, the concentration of the metal ions after concentration is 50 to 200 mmol/L.
An application of the metal ion transfer carrier or the metal ion transfer carrier prepared by the preparation method in a high-molecular film forming material.
In a preferred embodiment of the present invention, the polymeric film-forming material is an aqueous coating agent.
The high molecular film forming material also comprises a polyacrylate emulsion and a polyurethane emulsion film forming material.
The invention has the following beneficial effects:
the invention maintains the water solubility of the metal ion transfer carrier in a wider pH range by adjusting the dosage ratio of the substrate (the water-soluble compound containing the carboxyl group) and the metal ion, so that part of the carboxyl group of the water-soluble compound is combined with the metal ion through coordination, and the other part of the carboxyl group of the water-soluble compound exists in a free form in the solution. Therefore, the metal ion transfer carrier provided by the invention does not have the phenomenon of metal ion precipitation or uneven distribution under neutral or alkaline conditions.
The preparation method provided by the invention is simple, has low preparation cost, and can realize industrial production and application. The metal ion transfer carrier provided by the invention can be used for doping metal ions in a high-molecular film-forming material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a photograph of solutions of different concentrations of metal ion transfer carrier PAA-Zn at different pH values;
FIG. 2 shows ZnSO4AFM pictures of polyacrylic acid (PAA) and varying amounts of PAA-Zn (amounts representing the molar ratio of Zn ions to the total number of carboxyl groups of the finish components) added to a finish polyacrylate emulsion (PL); as can be seen from the AFM graph, the Zn ions added directly into the PL will precipitate slightly, while PAA-Zn added into the PL will not precipitate;
FIG. 3 shows ZnSO4Polyacrylic acid (PAA) and varying amounts of PAA-Zn (the amounts representing the molar ratio of Zn ions to the total number of carboxyl groups of the finish components) added to the finish polyacrylate emulsion (PL) for tensile properties after film formation; from the tensile property chart, when Zn ion is associated withWhen the molar ratio of the total carboxyl of the coating agent components is less than or equal to 1.5 percent, the tensile property of the PAA-Zn added into PL formed film is improved along with the increase of the PAA-Zn;
FIG. 4 shows ZnSO4Polyacrylic acid (PAA), and varying amounts of PAA-Zn (the amounts representing the molar ratio of Zn ions to the total number of carboxyl groups of the finish components) added to the finish polyacrylate emulsion (PL) to form a film; as is clear from the tear strength chart, when the molar ratio of Zn ions to the total carboxyl groups of the coating composition is 2.0% or less, the tear strength of the film formed by adding PAA-Zn to PL increases with the addition of PAA-Zn.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 125000g/mol, and an aqueous polyacrylic acid solution having a molar concentration of 48mmol/L was prepared;
(2) dissolving zinc sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 20mmol/L, and mixing uniformly. Adjusting the pH value of the mixed solution to 7 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 50mmol/L to obtain the metal ion transfer carrier.
Example 2
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 125000g/mol, and an aqueous solution of polyacrylic acid having a molar concentration of 55mmol/L was prepared;
(2) dissolving zinc sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of zinc ions in the mixed solution is 25mmol/L, and mixing well. Adjusting the pH value of the mixed solution to 8 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 60mmol/L to obtain the metal ion transfer carrier.
Example 3
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 100000g/mol, and an aqueous solution of polyacrylic acid having a molar concentration of 65mmol/L was prepared;
(2) dissolving copper sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of copper ions in the mixed solution is 10mmol/L, and mixing uniformly. Adjusting the pH value of the mixed solution to 7 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of copper ions is 60mmol/L to obtain the metal ion transfer carrier.
Example 4
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 8000g/mol, and an aqueous solution of polyacrylic acid having a molar concentration of 80mmol/L was prepared;
(2) dissolving nickel sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of nickel ions in the mixed solution is 15mmol/L, and uniformly mixing. Adjusting the pH value of the mixed solution to 8 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of nickel ions is 65mmol/L to obtain the metal ion transfer carrier.
Example 5
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in the embodiment, the water-soluble compound containing carboxyl is polyacrylic acid (PAA), the weight-average molecular weight is 110000g/mol, and polyacrylic acid aqueous solution with the molar concentration of 70mmol/L is prepared;
(2) dissolving zirconium sulfate in water, adding polyacrylic acid water solution to obtain mixed solution, and mixing zirconium ions (Zr) in the mixed solution4+) The molar concentration of (A) is 10mmol/L, and the mixture is uniformly mixed. Adjusting the pH value of the mixed solution to 9 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zirconium ions is 70mmol/L to obtain the metal ion transfer carrier.
Example 6
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 125000g/mol, and an aqueous solution of polyacrylic acid was prepared at a molar concentration of 200 mmol/L;
(2) dissolving zinc sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 30mmol/L, and mixing uniformly. Adjusting the pH value of the mixed solution to 8 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 80mmol/L to obtain the metal ion transfer carrier.
Example 7
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was polyacrylic acid (PAA), the weight average molecular weight was 125000g/mol, and an aqueous solution of polyacrylic acid was prepared at a molar concentration of 200 mmol/L;
(2) dissolving zinc sulfate in water, adding into polyacrylic acid water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 30mmol/L, and mixing uniformly. Adjusting the pH value of the mixed solution to 11 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 95mmol/L to obtain the metal ion transfer carrier.
Example 8
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in the present example, the water-soluble compound containing carboxyl groups was citric acid, the weight average molecular weight was 192g/mol, and an aqueous citric acid solution having a molar concentration of 50mmol/L was prepared;
(2) dissolving zinc sulfate in water, adding into citric acid water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 20mmol/L, and mixing well. Adjusting the pH value of the mixed solution to 10 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 50mmol/L to obtain the metal ion transfer carrier.
Example 9
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble compound containing carboxyl groups was tartaric acid, the weight-average molecular weight was 150g/mol, and an aqueous tartaric acid solution was prepared at a molar concentration of 60 mmol/L;
(2) dissolving zinc sulfate in water, adding into tartaric acid water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 25mmol/L, and mixing well. Adjusting the pH value of the mixed solution to 10 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 60mmol/L to obtain the metal ion transfer carrier.
Example 10
The embodiment provides a preparation method of a metal ion transfer carrier, which comprises the following steps in sequence:
(1) in this example, the water-soluble carboxyl group-containing compound was carboxymethylcellulose, the weight-average molecular weight was 90000g/mol, and an aqueous solution of carboxymethylcellulose was prepared at a molar concentration of 70 mmol/L;
(2) dissolving zinc sulfate in water, adding into carboxymethyl cellulose water solution to obtain mixed solution, wherein the molar concentration of metal zinc ions in the mixed solution is 10mmol/L, and mixing uniformly. Adjusting the pH value of the mixed solution to 10 by using 2.5mol/L sodium hydroxide solution;
(3) and concentrating the mixed solution by using a rotary evaporator until the concentration of zinc ions is 40mmol/L to obtain the metal ion transfer carrier.
Comparative example 1
This comparative example differs from example 1 only in that the molar concentration of metallic zinc ions in the mixed solution is different, in this comparative example, the molar concentration of metallic zinc ions is 30mmol/L, and the rest of the preparation process is the same.
Comparative example 2
This comparative example differs from example 1 only in that the molar concentration of metallic zinc ions in the mixed solution is different, in this comparative example, the molar concentration of metallic zinc ions is 40mmol/L, and the rest of the preparation process is the same.
Experimental example 1
The metal ion transfer carriers before concentration obtained in example 1, comparative example 1 and comparative example 2 were taken, respectively, the pH of each metal ion transfer carrier solution was adjusted to 2 to 11 with sulfuric acid and sodium hydroxide, respectively, and the precipitation of the solutions at different pH was observed, respectively.
As shown in fig. 1, it is clear from fig. 1 that the metal ion transfer support of example 1 did not precipitate at pH 2 to 11, and the solution was clear. In contrast, the metal ion transfer supports of comparative examples 1 and 2 were precipitated at pH 5 to 11, and the solutions were turbid. PAA-Zn represents a metal ion transfer carrier.
This indicates that an excess of metal ions results in a decrease in water solubility and precipitation.
Experimental example 2
ZnSO is added4Polyacrylic acid (PAA), various amounts of PAA-Zn (metal ion transfer vehicle) (amounts representing the molar ratio of Zn ions to the total number of carboxyl groups of the coating composition) were added to the coating polyacrylate emulsion (PL), respectively, and atomic force microscopy (AFM, Dimension ICON, Bruker, Germany) was performed, respectively.
Wherein PL/Zn1.5Group representation: ZnSO4Added to a coating agent polyacrylate emulsion (PL), and the molar ratio of Zn to the total number of carboxyl groups of the PL component in the mixed solution is 1.5%.
PL/PAA-Zn0.5Group representation: PAA-Zn was added to the coating agent polyacrylate emulsion (PL) in a molar ratio of Zn to the total number of carboxyl groups of the PL component of 0.5%.
PL/PAA-Zn1.0Group representation: PAA-Zn was added to the coating agent polyacrylate emulsion (PL) in a molar ratio of Zn to the total number of carboxyl groups of the PL component of 1.0%.
PL/PAA-Zn1.5Group representation: PAA-Zn was added to the coating agent polyacrylate emulsion (PL) in a molar ratio of Zn to the total number of carboxyl groups of the PL component of 1.5%.
PL/PAA-Zn2.0Group representation: PAA-Zn was added to the coating agent polyacrylate emulsion (PL) in a molar ratio of Zn to the total number of carboxyl groups of the PL component of 2.0%.
Referring to FIG. 2, it can be seen from FIG. 2 that when metal ions are added directly to the polyacrylate emulsion (PL), the surface appearance of the coating agent is poor. After the metal ion transfer carrier is introduced into the finishing agent, the surface appearance is good.
Experimental example 3
The tensile property of the coating agent prepared in the experimental example 2 after film formation is detected, the test method refers to the tensile property test method of GB/T13022-91 plastic films, and the result is as follows:
as shown in FIG. 3, it can be seen from FIG. 3 that the coating agent prepared by adding metal ions directly to the polyacrylate emulsion (PL) without adding metal ions to the PL or by directly mixing a water-soluble compound with PL exhibited poor tensile properties after film formation, while the coating agent prepared by introducing a metal ion transport carrier into the PL exhibited good tensile properties after film formation, and the higher the zinc content (within a certain range), the better the tensile properties.
Further, PL/PAA-Zn2.0The tensile properties of the groups are lower than PL/PAA-Zn1.5The reason for this group is that the Zn content is excessive, resulting in generation of a slight amount of precipitates, resulting in the influence of tensile properties.
Example 4
The tearing strength of the coating agent prepared in the experimental example 2 after film forming is detected, the testing method refers to the measurement of the tearing strength of GB/T529-:
as shown in FIG. 4, it can be seen from FIG. 4 that the coating agent prepared by directly adding metal ions to the polyacrylate emulsion (PL) without adding metal ions to the PL or by directly mixing a water-soluble compound with the PL exhibited poor tear strength after film formation, while the coating agent prepared by introducing a metal ion transport carrier into the coating agent exhibited high tear strength and exhibited high tear strength as the zinc content was increased.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
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