KR101088480B1 - Aniline-urea copolymers, and film made therefrom, and method for making thereof - Google Patents

Abstract

Aniline-urea copolymer, a film prepared therefrom, and a method of preparing the same are provided. The aniline-urea copolymer is represented by the following formula (1).

<Formula 1>

The aniline-urea copolymer is prepared by preparing a solution containing oligoaniline substituted with a protecting group and mixing a solution containing oligoaniline and a solution containing diisocyanate. Aniline-urea copolymers have good oxidative stability and solubility, which has the advantage of excellent processability in film production, and because they can be discolored and impart electrical activity by doping with acid at various potentials. Application to memory devices is possible.

Description

Aniline-urea copolymer, film prepared therefrom, and method for manufacturing same {Aniline-urea copolymers, and film made therefrom, and method for making etc}

The present invention relates to an aniline-urea copolymer, a film prepared therefrom, and a method for producing the same, and more particularly, to an aniline-urea copolymer having an excellent processability by improving solubility and oxidative stability, and a film prepared therefrom. It relates to a manufacturing method.

 Polyaniline, which is known as a conductive polymer, may be easily oxidized in air, especially in a moist environment, and care should be taken in synthesis and storage. In addition, since the flexibility of the molecular chain is reduced due to the conjugated structure, solubility in an organic solvent having a low boiling point is very low, not only in synthesis but also in process of producing a polyaniline film. Accordingly, there is a need for the development of a polymer that can provide improved oxidation stability and solubility while having electrical activity without destroying the conjugated structure, and an efficient method for producing a conductive polymer using the same.

The technical problem to be solved by the present invention is to provide an aniline-urea copolymer with improved processability.

Another technical problem to be solved by the present invention is to provide a conductive aniline-urea copolymer using an aniline-urea copolymer with improved processability.

One aspect of the present invention to achieve the above technical problem provides an aniline-urea copolymer represented by the following formula (1).

<Formula 1>

In Formula 1, X may be a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a substituted or unsubstituted C1-C24 hydrocarbon, n is a 2- to 23 It is an integer and m is an integer of 2-20.

In order to achieve the above technical problem, another aspect of the present invention provides a method for preparing an aniline-urea copolymer represented by Chemical Formula 1. The method includes preparing an oligoaniline represented by Formula 2 below and reacting the oligoaniline with a diisocyanate represented by Formula 3 below.

<Formula 2>

In Formula 2, X may be a t -butoxycarbonyl group ( t -BOC) or an acetyl group (CH ₃ CO), n is an integer of 2 to 23.

<Formula 3>

In Formula 3, R is a substituted or unsubstituted C1-C24 hydrocarbon.

Another aspect of the present invention to achieve the above technical problem provides an aniline-urea copolymer represented by the following formula (4).

<Formula 4>

In Chemical Formula 4, R is a substituted or unsubstituted C1-C24 hydrocarbon, a and b satisfy a + b = 1, L is an integer of 1 to 12, k is 0 or 1, m is It is an integer of 2-20.

Another aspect of the present invention to achieve the above technical problem provides a film comprising the aniline-urea copolymer represented by the formula (1).

Another aspect of the present invention to achieve the above technical problem provides a method for producing a film comprising the aniline-urea copolymer represented by the formula (1). The method may include dissolving the aniline-urea copolymer represented by Formula 1 in a solvent to form aniline-urea copolymer solution and applying the aniline-urea copolymer solution on a substrate to prepare a film. Can be. The method may further include immersing the prepared film in the protic acid solution, and further comprising heat treating the film before immersing the film in the protic acid solution.

The method may further comprise introducing a protic asset into the aniline-urea copolymer solution before applying the aniline-urea copolymer solution onto the substrate.

As described above, according to the present invention, the aniline-urea copolymer substituted with a protecting group exhibits improved oxidation stability and good solubility in an organic solvent having a low boiling point, and thus has excellent processability in manufacturing a film. In addition, since by-products are not generated during the polymerization process, it is very advantageous in terms of time and economy, and can be discolored and imparted electrical activity by doping with acid at various potentials, so that it can be applied to a color developing device, a sensor and an organic memory device. .

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Aniline with protecting group Urea  Copolymer production

Formula 1 represents an aniline-urea copolymer having a protecting group introduced therein according to an embodiment of the present invention.

<Formula 1>

In Formula 1, X may be a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a substituted or unsubstituted C1-C24 hydrocarbon, n is a 2- to 23 It is an integer and m is an integer of 2-20.

1 is a flow diagram illustrating a method of preparing the aniline-urea copolymer of Chemical Formula 1.

Referring to Figure 1, oligoaniline is prepared (S10). The oligoaniline is an organic compound represented by the following Chemical Formula 2, and, for example, aniline heptamer diamine, aniline pentamer diamime, aniline trimer diamine, and the like. Can be. The oligoaniline may be prepared in a state in which boiling points such as chloroform (CHCl ₃ ), methylene chloride (CH ₂ Cl ₂ ) and tetrahydrofuran (THF) are dissolved in a low polar aprotic organic solvent.

<Formula 2>

In Formula 2, X may be a t -butoxycarbonyl group ( t -BOC) or an acetyl group (CH ₃ CO), n is an integer of 2 to 23.

Wherein X is, aniline-urea in the manufacture and processing of the copolymers can serve to improve the solubility of the role with the same solvent to the protecting group to prevent the oxidation, preferably a t-butoxy carbonyl (t -BOC May be).

The oligoaniline and the diisocyanate represented by the following Chemical Formula 2 are reacted (S12).

<Formula 3>

In Formula 2, R is a substituted or unsubstituted C1-C24 hydrocarbon, for example dodecano diisocyanate, hexano diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate Can be. In the above reaction, the oligoaniline and the diisocyanate may be mixed in a molar ratio of 1: 0.95 to 1.05, preferably in a molar ratio of 1: 1. Here, the concentration of the mixed solution is preferably 1 to 20 w / v% concentration, but if the concentration is higher than the viscosity is difficult to react, the problem is that the molecular weight is lowered if the concentration is less than Because there is. In addition, in the step of reacting the oligoaniline with the diisocyanate, by stirring with appropriate heat, the reaction may be accelerated and the molecular weight of the resulting polymer may be increased. However, if the reaction temperature is too high, there is a need to reflux, so the heating temperature is appropriate from room temperature to 55 ℃.

Through the above process, the aniline-urea copolymer represented by Chemical Formula 1 may be obtained without by-products by the reaction between the primary amine of the oligoaniline and the diisocyanate (S14).

Thereafter, the polymerization is completed, the aniline-urea copolymer solution having a viscosity can be purified by a reprecipitation method by slowly dropping a polar protic organic solvent, such as methanol. In this case, before performing the reprecipitation method, a small amount of the same solvent as the solvent of the solution may be added to lower the viscosity of the aniline-urea copolymer solution to facilitate solution collection. When a solid material is produced through the reprecipitation method, the solid material may be filtered, washed, and dried to finally obtain aniline-urea copolymer in a solid state represented by Chemical Formula 1.

Aniline with protecting group removed Urea  Copolymer production

When the protecting group is removed from the aniline-urea copolymer represented by Chemical Formula 1, the leucoemeraldine base state (a = 1, b = 0) to obtain an aniline-urea copolymer.

When the aniline-urea copolymer of the leucoemeraldine base state (a = 1, b = 0) is oxidized, the emeraldine base state (a = 0.5, b = 0.5) or furnigra Aniline-urea copolymers in a pernigraniline base state (a = 0, b = 1) can be obtained.

<Formula 4>

In Chemical Formula 4, R is a substituted or unsubstituted C1-C24 hydrocarbon, a and b satisfy a + b = 1, L is an integer of 1 to 12, k is 0 or 1, m is It is an integer of 2-20. In the relationship between the above formula (1) and (4), n + 1 = 2L + k is satisfied.

Conductive Film Manufacturing (1)

2 is a flowchart illustrating a method of manufacturing a conductive aniline-urea copolymer film according to another embodiment of the present invention.

2, aniline-urea copolymer solution represented by Chemical Formula 1 is dissolved in a solvent to prepare aniline-urea copolymer solution (S20). The solvent may be a mixture of a polar protic organic solvent and a polar aprotic organic solvent. This is because when a polar aprotic organic solvent such as chloroform or methylene chloride is added alone, a gel of aniline-urea copolymer is formed due to strong hydrogen bonding between urea groups, so that only part of the gel is dissolved. This is because it is preferable to add a small amount in advance to prevent gel development, and then to add a polar aprotic organic solvent so that it can be completely dissolved. However, if the amount of the relatively polar protic organic solvent is higher, the aniline-urea copolymer does not completely dissolve and a precipitate is formed. Therefore, it is necessary to use the polar protic organic solvent only as a means for preventing gel formation. The proportion of protic solvent is preferably used in the range of 5 to 20 v / v% based on the total volume of the solvent.

The aniline-urea copolymer solution is applied on a substrate to prepare a film (S22). This can be done by a simple method of applying the solution onto a substrate and drying at room temperature. Here, a board | substrate includes the container, such as a petri dish used for manufacturing the board | substrate which can be used for an electronic element, and a freestanding film. In addition, it is preferable in view of the mechanical strength of the film that the concentration of the aniline-urea copolymer solution is 5 to 10 w / v%.

The film is heat-treated by adjusting a predetermined temperature and time at each temperature (S24). Thereby, a film including the aniline-urea copolymer represented by the formula (4) from which the protecting group is removed can be obtained. For example, under nitrogen atmosphere, heat treatment at 200 ℃ to 250 ℃ for 30 minutes to 1 hour, 185 ℃ to 195 ℃ for 2 hours to 2 hours 30 minutes and 175 ℃ to 180 ℃ 10 hours or more heat treatment at Aniline-urea copolymer in the state of leucoemeraldine base (a = 1, b = 0) can be obtained.

The film is immersed in the positive asset solution (S26). In this case, the proton may act as a dopant to dope the aniline-urea copolymer represented by the formula (4). As a result, conductivity may be imparted to the film.

However, the heat treatment step (S24) may be omitted when the film is thin so that the positive film can be penetrated into the positive asset when the film is immersed in the positive asset solution. In this case, the protecting group is removed by the introduction of the positive asset, and the aniline-urea copolymer represented by Formula 4 is formed, and since the positive asset acts as a dopant, the aniline-urea represented by Formula 4 finally. It is possible to produce a conductive film comprising a protic asset doped with a copolymer.

Conductive Film Manufacturing (2)

3 is a flowchart illustrating a method of manufacturing a conductive aniline-urea copolymer film according to another embodiment of the present invention.

Referring to FIG. 3, the aniline-urea copolymer solution containing the aniline-urea copolymer of Chemical Formula 1 is prepared in the same manner as described with reference to FIG. 2 (S30).

A positive asset is introduced into the aniline-urea copolymer solution (S32). The protic asset may be an organic sulfonic acid, and may be, for example, camphorsulfonic acid (CSA), dodecylbenzenesulfonic acid, or the like. By introducing a positive asset, the protecting group is removed and the aniline-urea copolymer represented by Formula 4 is formed, and since the positive asset acts as a dopant, the aniline-urea copolymer represented by Formula 4 is finally Conductive aniline-urea copolymers can be prepared that include doped protons.

In addition, by varying the molar ratio of the proton, which is a dopant, it is possible to give different conductivity depending on the level of doping. After introduction of the positive asset, the aniline-urea copolymer in the precipitate state is filtered, washed and dried, and then dissolved in a suitable organic solvent such as m -cresol or N -methylpyrrolidone to prepare aniline-urea copolymer solution.

The aniline-urea copolymer solution is applied on a substrate to prepare a film (S34). The film may be prepared by spin coating, dip coating, drop coating, or the like, and is a positive asset doped with an aniline-urea copolymer represented by Chemical Formula 4. It becomes possible to manufacture a conductive film comprising a.

As described above, since the protecting group-substituted aniline-urea copolymer prepared according to the above embodiment shows good oxidative stability and solubility, a freestanding film can be prepared by a simple process therefrom, and the concentration and amount By controlling the thickness of the film can be adjusted, there is an excellent workability. In addition, since by-products are not generated during the polymerization process, it is very advantageous in terms of time and economy, and can be discolored and imparted electrical activity by doping with acid at various potentials, so that it can be applied to a color developing device, a sensor and an organic memory device. .

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Synthesis Example 1

A solution containing oligoaniline was prepared by dissolving 0.995 g (0.792 mmol) of aniline heptamer diamine in which t -butoxycarbonyl group was substituted in secondary amine in 9.95 ml of chloroform, and a dodecanodiaisocyanate. 0.2 g (0.792 mmol) was dissolved in 2.0 ml of chloroform to prepare a solution containing diisocyanate. Mix the two solutions in a flame-dried Schlenk flask and seal with a rubber stopper to prevent the ingress of outside air and stir for 24 hours while maintaining the temperature of the oil bath at 45 ° C to 55 ° C. It was. When the polymerization was completed, a small amount of chloroform was added to the viscous solution to easily lower the viscosity for solution collection, and then slowly dropping a large amount of methanol (1 L) to purify the polymer by reprecipitation. After stirring the solution in this state for a sufficient time (more than 6 hours), the pale pink solid material was filtered out. Finally, the aniline-urea copolymer was prepared by drying for 24 hours at room temperature and vacuum.

4 is a graph showing ¹ H-NMR of the aniline-urea copolymer prepared according to Synthesis Example 1.

Referring to FIG. 4, in Formula 1, n is 6, and R is C12, indicating that an aniline-urea copolymer is synthesized.

<Manufacture example 1>

1 ml of methanol was previously added to 0.25 g of the aniline-urea copolymer prepared in Synthesis Example 1, followed by stirring for about 3 minutes to disperse the polymer well. 4 ml of chloroform was added thereto, followed by stirring for about 10 minutes to completely dissolve to prepare a solution having a concentration of 5 w / v%. The solution was dropped in a petri dish 5 cm in diameter and then slowly dried. After about 48 hours, the film formed using tweezers was lifted to obtain a freestanding film.

<Manufacture example 2>

The film prepared in Preparation Example 1 was heat-treated under nitrogen atmosphere for 1 hour at 242 ° C., 2 hours 30 minutes at 195 ° C., and 10 hours at 180 ° C. to remove the t -butoxycarbonyl group and reduce the leucoe. Aniline-urea copolymer film in the meraldine base state was obtained.

<Manufacture example 3>

Except that the film prepared in Preparation Example 1 was heat-treated in air, the same method as in Preparation Example 2 was carried out to obtain an aniline-urea copolymer film in the emeraldine-based state.

&Lt; Preparation Example 4 &

The emeraldine-based aniline-urea copolymer film prepared in Preparation Example 3 was immersed in an acid solution (1M hydrochloric acid solution) for 12 hours, then taken out, washed well with water and dried, and then aniline-urea copolymer in an emeraldine salt state. Film was obtained.

5 is a UV-Vis spectrum of each film prepared according to Preparation Examples 1 to 4.

Referring to FIG. 5, according to each preparation example, the aniline-urea copolymer (a) substituted with t -butoxycarbonyl group, the aniline-urea copolymer (b) in the leuomeraldine base state, and the emeraldine base state It can be seen that the aniline-urea copolymer (c) and the aniline-urea copolymer (d) in the emeraldine salt state were formed.

Production Example 5

To 0.005 g of the aniline-urea copolymer prepared in Synthesis Example 1, 0.1 ml of methanol was added, followed by stirring for about 3 minutes to disperse well. Next, 0.4 ml of chloroform was added, followed by stirring for about 10 minutes to completely dissolve. 0.004 g of camphorsulfonic acid was dissolved in a mixed solvent of methanol (0.1 ml) and chloroform (0.4 ml), and then added to the solution in which the aniline-urea copolymer was dissolved to bring the concentration of the aniline-urea copolymer solution to 0.5 w / v%. Maintained. The solution was stirred in an oil bath at 50 ° C. for 48 hours, and then the precipitate was filtered, washed sufficiently with methanol and chloroform, and dried at room temperature and vacuum for 24 hours to obtain a polymer. (Aniline-urea copolymer and camphorsulfonic acid) Molar ratio of 1: 5)

6A and 6B are UV-Vis spectra measured after dissolving a polymer prepared according to Preparation Example 5 in m -cresol and N -methylpyrrolidone, respectively. 6A and 6B, it can be seen that aniline-urea copolymer in the emeraldine salt state was formed by the introduction of camphor sulfonic acid in the aniline-urea copolymer prepared in Synthesis Example 1.

<Manufacture example 6>

A polymer was prepared by the same method as described in Preparation Example 5, except that the molar ratio of aniline-urea copolymer and camphorsulfonic acid was 1: 2, 1: 3, 1: 4 and 1 by varying the amount of camphorsulfonic acid. It was adjusted to 6: and the polymer for each was obtained.

Experimental Example 1

In Preparation Example 5 and Preparation Example 6, the conductivity of the polymer prepared at each molar ratio was measured. This is made by polymer pellets prepared in each molar ratio, the thickness of each pellet is measured by a micrometer, and then measured using a 4-point probe method.

7 is a graph showing the conductivity of each polymer measured according to Experimental Example 1. Referring to FIG. 7, it can be seen that the addition of camphorsulfonic acid in an amount of 2 moles or more relative to 1 mole of aniline-urea copolymer shows excellent conductivity of 2.1 × 10 ⁻⁵ S / cm or more. In particular, when the molar ratio of aniline-urea copolymer and camphorsulfonic acid is 1: 5, the best conductivity was 4.5x10 ^-4 S / cm.

Experimental Example 2

Aniline-urea copolymer substituted with t -butoxycarbonyl group prepared in Synthesis Example 1, aniline-urea copolymer from which the protecting group prepared in Preparation Example 2 was removed, and the emeraldine base state prepared in Preparation Example 3 The aniline-urea copolymer of, and the solubility of each of the solvents of the aniline-urea copolymer in the emeraldine salt state prepared in Preparation Example 4 were observed in Table 1 below.

[Table 1]

Synthesis Example 1 Production Example 2 Production Example 3 Preparation Example 4 Aniline-urea copolymer substituted with t -butoxycarbonyl group Aniline-urea copolymer without t -butoxycarbonyl group Aniline-urea copolymer in the emeraldine base state Aniline-urea copolymer in emeraldine salt state N -methylpyrrolidone Melts Does not melt Melts Melts Methylene chloride Melts Does not melt Does not melt Does not melt chloroform Melts Does not melt Does not melt Does not melt

Referring to Table 1, the aniline-urea copolymer substituted with t -butoxycarbonyl group is not only high boiling point N -methylpyrrolidone (bp 203 ° C.) but also low boiling point methylene chloride (bp 40 ° C.) or chloroform. It melts well even at (bp 61 ℃). However, the aniline-urea copolymers of Preparation Examples 2 to 4 in which t -butoxycarbonyl group is removed are not dissolved in methylene chloride or chloroform having a low boiling point. In general, polyaniline is also insoluble in solvents other than N -methylpyrrolidone. Therefore, it can be seen that the introduction of the t -butoxycarbonyl group can improve not only oxidation stability but also solubility in a low boiling point solvent, thereby improving processability in manufacturing films and the like.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. You can change it.

1 is a flowchart illustrating a method of preparing the aniline-urea copolymer of Chemical Formula 1.

2 and 3 are a flow chart showing a method for producing a conductive aniline-urea copolymer film, respectively.

4 is a graph showing ¹ H-NMR of the aniline-urea copolymer prepared according to Synthesis Example 1. FIG.

5 is a UV-Vis spectrum of each film prepared according to Preparation Examples 1-4.

6A and 6B are UV-Vis spectra measured after dissolving a polymer prepared according to Preparation Example 5 in m -cresol and N -methylpyrrolidone, respectively.

7 is a graph showing the conductivity of each polymer measured according to Experimental Example 1. FIG.

Claims (8)

Aniline-urea copolymer represented by the following formula (1): <Formula 1>

In Formula 1, X is a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a hydrocarbon of C1-C24, n is an integer of 2 to 23, m is 2 to It is an integer of 20. Preparing an oligoaniline represented by Formula 2 below; And Method for preparing an aniline-urea copolymer comprising the step of reacting the oligoaniline and the diisocyanate represented by the following formula (3): <Formula 1>

In Formula 1, X is a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a hydrocarbon of C1-C24, n is an integer of 2 to 23, m is 2 to It is an integer of 20. <Formula 2>

In Formula 2, X is a t -butoxycarbonyl group ( t -BOC) or an acetyl group (CH ₃ CO), n is an integer of 2 to 23. <Formula 3>

In Chemical Formula 3, R is a C1-C24 hydrocarbon. Aniline-urea copolymer represented by the following formula (4): <Formula 4>

In Formula 4, R is a hydrocarbon of C1 ~ C24, a and b satisfy a + b = 1, l is an integer of 1 to 12, k is 0 or 1, m is an integer of 2 to 20 to be. A film comprising the aniline-urea copolymer represented by the following formula (1): <Formula 1>

In Formula 1, X is a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a hydrocarbon of C1-C24, n is an integer of 2 to 23, m is 2 to It is an integer of 20. Dissolving the aniline-urea copolymer represented by Formula 1 in a solvent to form aniline-urea copolymer solution; And Aniline-urea copolymer film manufacturing method comprising the step of applying aniline-urea copolymer solution on a substrate to prepare a film: <Formula 1>

In Formula 1, X is a t -butoxycarbonyl group ( t- BOC) or an acetyl group (CH ₃ CO), R is a hydrocarbon of C1-C24, n is an integer of 2 to 23, m is 2 to It is an integer of 20. The method of claim 5, The film manufacturing method further comprises the step of immersing the prepared film in the positive asset solution. The method of claim 6, Before immersing the film in the protic solution solution, The film manufacturing method further comprises the step of heat-treating the film. The method of claim 5, Before applying the aniline-urea copolymer solution onto a substrate, The method of manufacturing a film further comprising the step of introducing a protic asset in the aniline-urea copolymer solution.

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