KR100627470B1 - Preparing method for soluble microemulsion polymer of polyaniline-co-oanthranilic acid, the microemulsion polymer prepared thereby and steel or metal products having the same - Google Patents

Abstract

The present invention relates to a process for preparing a soluble poly (aniline-co-anthranic acid) microemulsion polymer, to a poly (aniline-co-anthranilic acid) microemulsion polymer prepared therefrom and to a steel or metal product to which such microemulsion polymer is applied.

[Formula 1]

Mixing anthranilic acid with aniline in a molar weight ratio of 1: 99-99: 1 and dissolving it in 1-10 wt% in an organic solvent at -10 to 80 ° C;

Preparing the mixture into a micelle-formed microemulsion solution using a surfactant; And

Gradually adding an oxidant at a flow rate of 0.01 to 10 ml / min at -10 to 50 ° C. such that a mixture of anthranilic acid and aniline in the microemulsion solution to the molar ratio of 1: 5 to 5: 1;

There is provided a process for preparing a soluble poly (aniline-co-anthranic acid) micro emulsion polymer.

There is also provided a soluble poly (aniline-co-anthranilic acid) micro emulsion polymer prepared by the process and steel or metal products to which such polymers have been applied.

According to the present invention it is possible to produce conductive polymers in the form of microemulsions which can be used as new steel sheet coatings, which can replace current chromate steel sheet coatings.

Aniline, anthranilic acid, conductive polymer, microemulsion polymer, steel sheet

Description

Process for preparing soluble poly (aniline-co-anthranilic acid) microemulsion polymers, microemulsion polymers prepared therefrom and steel or metal products to which such microemulsion polymers are applied. ), THE MICROEMULSION POLYMER PREPARED THEREBY AND STEEL OR METAL PRODUCTS HAVING THE SAME}

The present invention relates to a process for preparing poly (aniline-co-oanthranilic acid) microemulsion polymers, microemulsion polymers prepared therefrom and steel or metal products to which such microemulsion polymers are applied. More specifically, a method of preparing a poly (aniline-co-anthranilic acid) microemulsion polymer which is excellent in water solubility, an improved doping method, and which can replace a chromate coating, a microemulsion polymer prepared therefrom and such a microemulsion polymer To steel or metal products applied.

Polyaniline is an electrically conductive polymer for various applications. Among conductive polymers such as polyacetylene, polythiophene and polypinol, polyaniline has been studied a lot because the stability in the air and the electrical properties of aniline can be controlled by the oxidation state of the main chain. However, polyaniline, like other conductive polymers, has a disadvantage in that solubility is very low. So what has been studied is polyaniline with a side branch like polyanthranilic acid. However, this polyaniline also has a disadvantage in that it is well soluble in organic solvents but not in water. The water-soluble conductive polymer is environmentally friendly and can be used in various applications such as being able to replace chromate plating of iron sheets.

Cold rolled steel plate is mainly plated with zinc, nickel, zinc-nickel alloy, tin, etc., and is post-treated with chromate to prevent corrosion, improve durability, and improve workability. However, the hazards and environmental pollution of the materials used for these plating and chromium treatments are serious problems, and there is an urgent need for environmentally friendly surface treatment materials and surface treatment chemistry techniques that can supplement or replace them. have. The conductive polymer is an organic material, which is environmentally friendly and has conductivity, and is expected to replace the chromate coating as well as to be used complementarily with the plating layer. However, since such conductive polymers do not dissolve in most solvents, their application possibilities are very small. Therefore, it is necessary to develop a material capable of improving solubility by attaching specific functional groups to such conductive polymers.

In general, the synthesis of polyaniline is accomplished by chemical oxidative polymerization in an aqueous solution. This method yields polyaniline precipitated after several hours under aniline, acid, oxidizing agent and low temperature (about 5 ° C.) conditions. The polyaniline thus synthesized is mostly amorphous, difficult to process, and insoluble in most organic solvents or water. However, polyaniline prepared by the emulsion method has the property of dissolving in water differently. In emulsion polymerization, when the surfactant is added above the critical micelle concentration, about 10 to 1000 surfactants are collected to form micelles. The micelles thus formed are polymerized by reaction with radicals. The emulsion polymerization of polyaniline is here polymerized with aniline, acid and oxidant mixed with water and using nonpolar or weak polar liquids such as xylene, chloroform and toluene. The polymers thus prepared can be used in applications in water-soluble state without any other process.

Accordingly, an object of the present invention is to provide a method for producing a microemulsion polymer of polyaniline and polyanthranilic acid dissolved in water using aniline and anthranilic acid monomer as raw materials.

Another object of the present invention is to provide a poly (aniline-co-anthranlic acid) micro emulsion polymer prepared by the above method.

It is a further object of the present invention to provide a steel or metal product to which the poly (aniline-co-anthranilic acid) microemulsion polymer is applied.

According to one aspect of the invention,

Mixing anthranilic acid with aniline in a molar weight ratio of 1: 99-99: 1 and dissolving it in 1-10 wt% in an organic solvent at -10 to 80 ° C;

Preparing the mixture into a micelle-formed microemulsion solution using a surfactant; And

Gradually adding an oxidant at a flow rate of 0.01 to 10 ml / min at -10 to 50 ° C. such that a mixture of anthranilic acid and aniline in the microemulsion solution to the molar ratio of 1: 5 to 5: 1;

There is provided a method for preparing a soluble poly (aniline-co-antranylic acid) micro emulsion polymer.

According to the second aspect of the present invention,

A poly (aniline-co-anthranilic acid) micro emulsion polymer having a molecular weight of 1,000-2,500,000 prepared by the above method is provided.

According to the third aspect of the present invention,

Provided is a steel or metal product to which the poly (aniline-co-anthranilic acid) microemulsion polymer is applied.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, a mixture of anthranilic acid and aniline of formula 1 is dissolved in an organic solvent at -10 to 80 ° C, and stabilized by using a surfactant.

The mixing ratio of the anthranilic acid to aniline is 1: 99-99: 1 molar weight% ratio, preferably 10: 90-80: 20 molar weight% ratio. If the mixing ratio of anthranilic acid to aniline is out of the above range, the physical properties of the poly (aniline-co-anthranylic acid) microemulsion polymer tend to be slightly lowered, and the reaction is long, and the molecular weight and yield are low. Acid and aniline are mixed with a comonomer to polymerize.

Then, the mixture of anthranilic acid and aniline is dissolved in an organic solvent, wherein the temperature of the mixed solvent is -10 to 80 ° C. If the temperature is less than -10 ° C, the anthranilic acid and aniline are not dissolved. If the temperature is over 80 ° C, the molecular weight is lowered to obtain a polymer. Low molecular weight polymers are undesirable because they are not suitable as conductive polymeric materials for steel sheets. The poly (aniline-co-anthranilic acid) microemulsion polymers of the present invention are suitable for use as conductive polymer materials applied to steel sheets and have a molecular weight of 1,000-2,500,000, commonly known as the polymer range.

In addition, when the mixture of anthranilic acid and aniline is mixed with an organic solvent, an organic solvent in which water is mixed with an organic solvent may be used, in which case the mixing ratio of water to organic solvent in the mixed solvent of water and organic solvent is 1: 50-. 50: 1 range. The reason for limiting the mixing ratio of water and organic solvent is that if the mixing ratio of water to organic solvent is less than 1:50, the amount of water is too small to dissolve the anthranilic acid. This is due to the lack of aniline dissolution. Since the aniline is well dissolved in the organic solvent and anthranilic acid tends to be well dissolved in water, the higher the ratio of the aniline, the higher the ratio of the organic solvent, and the higher the ratio of the anthranilic acid, the higher the water ratio. The organic solvent may be any organic solvent capable of dissolving aniline and includes, for example, chloroform, methylene chloride, tetrahydrofuran, alcohol, xylene, enmethylpyrrolodione and dimethyl sulfoxide.

In addition, when dissolving the mixture of aniline and anthranilic acid in an organic solvent, the mixture of aniline and anthranilic acid is mixed at 1-10% by weight based on the total weight of the organic solvent and the mixture of the aniline and anthranilic acid. If the mixture of aniline and anthranilic acid is less than 1% by weight, the amount of monomer is too small, and the polymerization process time is too long, and when mixed with more than 10% by weight, it may not be sufficiently dissolved in the organic solvent. Can be.

Then, a mixture of aniline and anthranilic acid dissolved in the organic solvent is formed into a microemulsion solution in which micelles are formed using a surfactant. Surfactants used in the present invention are dodecylbenzenesulfonic acid, camphorsulfonic acid, sodium dodecylbenzenesulfate, sulfosalicylic acid, toluenesulfonic acid, benzenesulfonic acid, sulfemic acid, naphthalenesulfonic acid, dimethylsulfate, diethylsulfate, dipropylsulfate Pate, di (2-ethylhexyl) sulfoxynate, 4-sulfophthalic acid, malonic acid and twinseries. The surfactant is preferably mixed at 0.1-10% by weight of the total weight. If the surfactant is less than 0.1% by weight or 10% by weight or more, the emulsion solution may not be stabilized.

On the other hand, separately prepared by dissolving an oxidant which is a synthesis catalyst in a solvent. Preferably prepared by dissolving in water of -10 ~ 50 ℃ or mixed solvent of water and organic solvent. In addition, the oxidizing agent used in the present invention may be selected from the group consisting of ammonium persulfate, FeCl ₃ , CuCl ₂ , Cu (BF ₄ ) ₂ , Cu (ClO ₄ ) ₂ and K ₂ Cr ₂ O ₇ , It is preferable to prepare by dissolving 1-10% by weight in a mixed solvent of an organic solvent, because the oxidant can be completely dissolved within this range. And the oxidant is also preferably 1: 5-5: 1 in a molar ratio of the mixture of anthranilic acid and aniline to the oxidant in the microemulsion solution. If the amount of the oxidizing agent is out of the range, there is a problem that the polymerization process time for the polymerization of the monomer of anthranilic acid and aniline in the microemulsion solution is too long. In the case of using such an oxidizing agent, the reaction time of the monomer and the oxidizing agent is determined by the color change that becomes light yellow when the monomer (s) is completely dissolved in a mixed solvent of water and an organic solvent. In addition, the solvent used at this time is about 20% less than the amount used to polymerize the general aniline-based material in order to increase the probability of the reaction and to have a rapid reaction and a higher molecular weight. In addition, when preparing the oxidizing agent, it is preferable that the temperature of the solvent be -10 to 50 ° C. If the temperature is less than -10 ° C, the polymerization of anthranilic acid and aniline does not occur. Because you can not get. In addition, if the oxidizing agent is dissolved in a mixed solvent of water and an organic solvent, the mixing ratio of water to organic solvent is preferably 1: 50-50: 1, because the mixing ratio of water to organic solvent is less than 1:50. The amount is so small that it is not enough to dissolve anthranilic acid, and if it is 50: 1 or more, the amount of organic solvent is too small to dissolve aniline.

The solution containing the oxidant is gradually added to the microemulsion solution in which the micelle is prepared as described above. At this time, since the exothermic reaction occurs as the oxidant solution is added, the microemulsion of the oxidant solution at a slow flow rate of 0.01-10 ml / min in order to prevent the possibility of side reactions that may occur due to the rapid rise of the temperature of the reactant by such exothermic reaction Preference is given to adding to the solution. If the addition rate of the solution containing the oxidizing agent is added to less than 0.01ml / min, the addition rate is too slow and takes a long time and when added at a rate of 10ml / min or more may cause side reactions to rise rapidly. .

Then, the mixed solution of the anthranilic acid and aniline (the micro emulsion solution) to which the oxidant is added is polymerized at -10 to 50 ° C for 5 to 48 hours. If the polymerization temperature is less than -10 ℃ polymerization does not occur, if the 50 ℃ or more there is a problem that the molecular weight is lowered, 10 ~ 50 ℃ is appropriate, if the polymerization time is less than 5 hours the reaction is not completely terminated, the molecular weight is lowered If it is more than 48 hours, the reaction is completely completed and there is no change, so the polymerization time of 5-48 hours is appropriate.

Soluble poly (aniline-co-anthranilic acid) microemulsion polymers prepared according to the present invention generally have a molecular weight of 1,000-2,500,000 in the polymer range, intrinsic viscosity of 0.01-3.00dL / g, and electrical conductivity of 10-6 ~ 10S / cm and thermal stability of at least 200 ℃, suitable for environmentally friendly replacement of chromate coatings on steel or metal products requiring corrosion protection, solubility with organic solvents, good thermal stability and ease of film making .

As described above, the present invention provides a new conductive polymer material exhibiting properties that can be used as a new steel sheet coating material, and the polymer of the present invention is excellent in intrinsic viscosity, corrosion resistance, solubility with organic solvents, and thermal stability. It can be used for other coating or plating applications.

Hereinafter, the present invention will be described in detail through examples.

Example 1

2 g (0.021 mol) of aniline and 3 g (0.022 mol) of anthranilic acid were dissolved in a 50 ml organic solvent (xylene: ethanol = 1: 1) at room temperature. 14 g (0.043 mol) of dodecylbenzenesulfonic acid was dissolved in 200 ml of water, and then added to the mixed solution of aniline and anthranilic acid. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was transferred back to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing aniline and anthranilic acid at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified using nuclear magnetic resonance spectra (NMR). The emulsion solution turned green may be applied to the glass plate or iron plate coating as a conductive polymer material.

Example 2

2 g (0.021 mol) of aniline and 3 g (0.022 mol) of anthranilic acid were dissolved in a 50 ml organic solvent (xylene: ethanol = 1: 1) at room temperature. 9.9 g (0.043 mol) of camphorsulfonic acid and 12.4 g of sodium dodecyl sulfate were dissolved in 200 ml of water, and then added to the mixed solution of aniline and anthranilic acid. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was again transferred to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing the aniline and anthranilic acid at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified using nuclear magnetic resonance spectra (NMR). The emulsion solution turned green may be applied to the glass plate or iron plate coating as a conductive polymer material.

Comparative Example 1

5 g (0.054 mol) of aniline was dissolved in 50 ml of an organic solvent (xylene: ethanol = 1: 1) at room temperature. 17.6 g (0.054 mol) of dodecylbenzenesulfonic acid was dissolved in 200 ml of water and then added to the aniline solution. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was again transferred to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing aniline at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified by nuclear magnetic resonance spectra (NMR).

Comparative Example 2

7.4 g (0.054 mol) of anthranilic acid was dissolved in 50 ml of an organic solvent (xylene: ethanol = 1: 1) at room temperature. 17.6 g (0.054 mol) of dodecylbenzenesulfonic acid was dissolved in 200 ml of water and added to the anthranilic acid solution. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was again transferred to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing anthranilic acid at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified using nuclear magnetic resonance spectra (NMR).

Comparative Example 3

5 g (0.054 mol) of aniline was dissolved in 50 ml of an organic solvent (xylene: ethanol = 1: 1) at room temperature. 12.5 g (0.054 mol) of camphorsulfonic acid and 15.6 g (0.054 mol) of sodium dodecyl sulfate were dissolved in 200 ml of water and added to the aniline solution. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was again transferred to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing aniline at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified using nuclear magnetic resonance spectra (NMR).

Comparative Example 4

7.4 g (0.054 mol) of anthranilic acid was dissolved in 50 ml of an organic solvent (xylene: ethanol = 1: 1) at room temperature. 17.6 g (0.054 mol) of camphorsulfonic acid and 15.6 g of sodium dodecyl sulfate were dissolved in 200 ml of water and added to the anthranilic acid solution. The solution was then mixed for 20 minutes at 15000 rpm using a grinder to disperse the organic solvent layer and the water layer. The mixed solution was again transferred to a round flask, then put into a stirrer and stirred at 800 rpm. At this time, the temperature was maintained at 0 ℃. Separately, 9.8 g (0.042 mol) of ammonium persulfate, an oxidizing agent, was dissolved in 10 ml of water at 0 ° C. The solution containing the oxidant was added to the solution containing anthranilic acid at a flow rate of 0.01-1 ml / min while stirring with a magnetic stirrer and left for 24 hours. The result changed from white to blue to green.

After completion of the reaction, the solution was precipitated in 300 ml of methanol, filtered using a vacuum flask, and dried in a vacuum oven at room temperature for 12 hours. The result was a very dark brown material, which was identified using nuclear magnetic resonance spectra (NMR). The emulsion solution turned green may be applied to the glass plate or iron plate coating as a conductive polymer material.

Polyaniline prepared by the general synthesis is insoluble in most solvents, so it is difficult to apply the coating, but the soluble poly (aniline-co-anthranilic acid) microemulsion polymer prepared by the method of the present invention is dissolved in an aqueous layer. Therefore, it can be expected to be easily made when coating the glass or iron plate.

According to the present invention, an anthranilic acid and aniline can be used to prepare a conductive polymer by a microemulsion polymerization method. The conductive polymer in the form of a microemulsion of the present invention can be used as a new steel plate coating material to replace the current chromate. can do.

Claims (7)

[Formula 1]

Mixing anthranilic acid with aniline in a molar weight ratio of 1: 99-99: 1 and dissolving it in 1-10 wt% in an organic solvent at -10 to 80 ° C; Preparing the mixture into a micelle-formed microemulsion solution using a surfactant; And Gradually adding an oxidant at a flow rate of 0.01 to 10 ml / min at -10 to 50 ° C. such that the mixture of anthranilic acid and aniline in the microemulsion solution to the molar ratio of 1: 5 to 5: 1; Method for producing a soluble poly (aniline-co-anthranlic acid) micro emulsion polymer for coating a steel sheet. The steel sheet coating of claim 1, wherein the oxidant is selected from the group consisting of ammonium persulfate, FeCl ₃ , CuCl ₂ , Cu (BF ₄ ) ₂ , Cu (ClO ₄ ) _2, and K ₂ Cr ₂ O ₇ . A process for preparing a soluble poly (aniline-co-anthranilic acid) micro emulsion polymer. The method of claim 1, wherein the surfactant is dodecylbenzenesulfonic acid, camphorsulfonic acid, sodium dodecylbenzenesulfate, sulfosalicylic acid, toluenesulfonic acid, benzenesulfonic acid, sulfic acid, naphthalenesulfonic acid, dimethylsulfate, diethylsulfate, di Soluble poly (aniline-co-anthranilic acid) microemulsion polymer for steel plate coating, characterized in that it is selected from the group consisting of propylsulfate, di (2-ethylhexyl) sulfoxynate, 4-sulfophthalic acid, malonic acid and twin series Manufacturing method. The method of claim 1, wherein the anthranilic acid and aniline are mixed in a molar weight ratio of 10: 90-80: 20. The method of claim 1, wherein the organic solvent is selected from the group consisting of chloroform, methylene chloride, tetrahydrofuran, alcohol, xylene, ethylenepyrrolodione and dimethyl sulfoxide, soluble poly (aniline-coated) Anthranilic acid) microemulsion polymer preparation method. A poly (aniline-co-anthranilic acid) microemulsion polymer for coating a steel sheet having a molecular weight of 1,000-2,500,000 produced by the method of any one of claims 1 to 5. delete