KR20130030498A - Polynorbornenedicarboximide film modified with monochlorophenyl and method for producing the same - Google Patents

Abstract

PURPOSE: Monochlorophenyl group-containing polynorbornene dicarboximide is provided to produce a polynorbornene dicarboximide film with high heat resistance and transparency. CONSTITUTION: A method for preparing monochlorophenyl group-containing polynorbornene dicarboximide comprises: a step of converting endo-isomer norbornenecarboxylic anhydride into exo-isomer norbornenecarboxylic anhydride; a step of synthesizing the exo-isomer norbornenecarboxylic anhydride into N-monochlorophenyl norbornene carboxyimide; and a step of polymerizing the N-monochlorophenyl norbornene carboxyimide.

Description

Polynorbornenedicarboximide containing monochlorophenyl group and its manufacturing method {Polynorbornenedicarboximide film modified with monochlorophenyl and Method for producing the same}

The present invention relates to a polynorbornene dicarboxyimide film comprising a monochlorophenyl group having a flexible and high thermal stability and transparency, and an organic electroluminescent device using the same.

As the modern industrial society develops into a high information age, the importance of the electronic display industry that visualizes and transmits various information from various devices to human beings is increasing. In particular, ultra-lightweight, paper-like and thin flexible displays are the next generation displays. As much research is being done as.

In order to implement such a flexible display, various technologies are required in combination, and among them, a flexible substrate is recognized as the most important component that determines the performance of the display. Such flexible substrates require high heat resistance, transparency, low moisture permeability and good chemical resistance properties.

Polymeric materials have the disadvantage of being weak to heat, but they are gaining attention as flexible display materials in the future because they are transparent, flexible, light, and cheaper than other materials. As polymer flexible substrate material, polyethylene naphthalate (PEN) film with improved heat resistance, polycarbonate (PC) film with excellent transparency and heat resistance, and polyether sulfone (PES) with better heat resistance than polycarbonate are used as flexible substrate. Many studies have been conducted, and the use of polyimide (PI), cyclic olefin copolymer (COC), and polyarylate (PAR) is also being investigated.

However, the above polymers do not satisfy all of high heat resistance, high transparency, excellent chemical resistance and low water permeability.

On the other hand, Korean Patent Publication No. 1989-0000559 discloses the synthesis of polynorbornene dicarboxyimide in which the N-position of the imide is substituted with phenyl. However, the material has only been studied for its potential as an excellent gas-selective film, and has not yet been mentioned for its optical properties and its application as a substrate for flexible organic electroluminescent devices.

Republic of Korea Patent Publication No. 2007-78813 Republic of Korea Patent Publication No. 2007-11281 Japanese Patent Laid-Open No. 2006-54098 Japanese Patent Laid-Open No. 2003-231198

Accordingly, an object of the present invention is to provide a polynorbornene dicarboxyimide film having a higher heat resistance and transparency than a conventional transparent polymer film, and an organic electroluminescent device using the same.

According to one aspect of the present invention, an N-monochlorophenylnorbornenedicarboxyimide monomer having the following formula is provided.

According to another aspect of the present invention, there is provided a polynorbornene dicarboxyimide having the formula: wherein the N position of the imide is substituted with a monochlorophenyl group.

According to another aspect of the present invention, indium tin oxide (ITO) or zinc oxide (ITO) formed on a transparent film formed by drying the poly (N-monochlorophenylnorbornenedicarboxyimide) in a sheet form as a substrate is used as a substrate. ZnO), and an organic electroluminescent device comprising a hole transport layer, an electron transport layer, and a cathode sequentially deposited on the indium tin oxide or zinc oxide.

According to another aspect of the invention, the first step of converting the endo isomer norbornene dicarboxylic hydride to the exo isomer norbornene dicarboxylic hydride; A second step of synthesizing norbornenedicarboxylic anhydride of the exo isomer with N-monochlorophenylnorbornenedicarboxyimide; And a third step of polymerizing the synthesized N-monochloronorbornenedicarboxyimide to synthesize poly (N-monochlorophenylnorbornenedicarboxyimide). Provided is a method for preparing a mead.

Preferably, the first step, after heating the endo isomer is norbornene dicarboxylic anhydride to 220 ℃ or more in a nitrogen atmosphere, and slowly cooled to 120 ℃; At 120 ° C., adding chlorobenzene to the polynorbornenedicarboxylic anhydride to form a mixture; After cooling the mixture to room temperature, the crystals are filtered, washed and dried.

Preferably, the second step comprises the steps of: dissolving the norbornenedicarboxylic hydride of the exo isomer in toluene; Adding and stirring chloroaniline to the norbornenedicarboxylic hydride solution; Filtering and drying to form amic acid when the suspension is formed while stirring; And stirring the amic acid in sodium acetate anhydride, acetic anhydride solvent, refluxing, and recrystallization with methanol.

Preferably, the molar ratio of the amic acid, sodium acetate anhydride, and acetic anhydride may be 7: 4: 64.

Preferably, the third step comprises the steps of dissolving N-monochlorophenylnorbornenedicarboxyimide in a dichloroethane solvent in a nitrogen atmosphere as a polymerization initiator; Stopping the reaction by adding ethylvinyl ether in a nitrogen atmosphere; Precipitating by adding hexane at room temperature; Dissolving the precipitate in chloroform, hydrochloric acid and then hexane to reprecipitate; And drying the reprecipitate.

According to another aspect of the present invention, a polynorbornene dicarboxyimide film prepared by the above production method having a transparent and flexible, the N-position of the imide is substituted with a monochlorophenyl group; Indium tin oxide (ITO) or zinc oxide (ZnO) deposited by sputtering on the film; There is provided an organic electroluminescent device comprising a hole transport layer, an electron transport layer, and a cathode sequentially deposited on the indium tin oxide or zinc oxide.

According to the said structure, the polynorbornene dicarboxyimide film which has higher heat resistance and transparency than the existing transparent polymer film can be provided.

1 is a photograph showing an example of a flexible and transparent poly (N-monochlorophenylnorbornenedicarboxyimide) film.
Figure 2 shows the results of measuring the thermal stability of the poly (N- monochlorophenyl norbornene dicarboxyimide) polymer film by TGA of TA Instrument.
Figure 3 shows the results of measuring the glass transition temperature (T _g ) through DSC.
Figure 4 shows the optical properties of the polymer film through a UV-visible spectrometer.
5 shows the mechanical properties of the polymer film according to the present invention through a universal testing machine (UTM).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The present invention provides a newly synthesized N- (chloro)-(5-norbornene-2,3 dicarboxyimide) monomer and a poly (N-monochloro) that is a homopolymer polymerized using the monomer. Phenylnorbornenedicarboxyimide).

Ⅰ. Synthesis of polynorbornenedicarboxyimide containing monochlorophenyl group at N position of imide

1) Conversion of the endo isomer, norbornenedicarboxylic anhydride, to the exo isomer

The endo isomer, norbornenedicarboxylic anhydride, is placed in a two-necked round flask to make the interior nitrogen atmosphere. After heating at 220 ° C. for about 1 hour, the mixture is slowly cooled to 120 ° C. When it reaches 120 degreeC, chlorobenzene is added in 2 times molar ratio of polynorbornene dicarboxylic anhydride. After cooling to room temperature, the white crystals are filtered off, washed with hexane and dried in a vacuum oven at 60 ℃.

2) Synthesis of N-Monochlorophenylnorbornenedicarboxyimide Monomer

Referring to the following reaction scheme, first, the norbornenedicarboxylic hydride of the exo isomer is sufficiently dissolved in toluene. At this time, the concentration of the solvent is to be 10% by weight.

Subsequently, 5% of the reaction product of monochloroaniline dissolved in toluene is added to the molar number of the norbornene monomer, and dropped dropwise into the norbornenedicarboxylic hydride solution by stirring at 60 ° C. for 3 hours. Once the suspension is made, it is filtered, washed with toluene and dried in a vacuum oven at 60 ° C.

The obtained amic acid is stirred and refluxed with anhydrous acetic acid solvent for 2 hours with sodium anhydride. At this time, the molar ratio of amic acid, sodium anhydride, and acetic anhydride is preferably 7: 4: 64.

After cooling to room temperature, the obtained crystals can be washed several times with water and recrystallized twice with methanol to obtain an N-monochlorophenylnorbornenedicarboxyimide monomer as shown in [Formula 1].

3) Synthesis of Poly (N-Monochlorophenylnorbornenedicarboxyimide)

Referring to the reaction scheme below, the N-monochlorophenylnorbornenedicarboxyimide monomer is completely dissolved in a dichloroethane solvent.

At this time, the concentration of the solvent is 15% by weight, a metal catalyst is used as the polymerization initiator, for example, a ruthenium catalyst such as [Formula 2] may be used.

Here, "P (C _Y ) ₃ " means Tricyclohexylphosphine.

The metal catalyst is added to the dichloroethane solution in which the monomer is completely dissolved, and reacted at 60 ° C. for 4 hours in a nitrogen atmosphere. Termination of the polymerization is achieved by adding ethylvinyl ether in a nitrogen atmosphere. After cooling to room temperature, the polymerized solution is precipitated in an excess of hexane to solidify, the polymer is dissolved in chloroform, and a few drops of 1 normal hydrochloric acid are added. Then precipitated again in hexane to solidify and dried in 60 ℃ vacuum oven. After this process 2-3 times, a pure poly (N-monochlorophenylnorbornenedicarboxyimide) polymer can be obtained.

Ⅱ. Preparation of Poly (N-Monochlorophenylnorbornenedicarboxyimide) Film

10% by weight of poly (N-monochlorophenylnorbornenedicarboxyimide) polymer was dissolved in N, N-dimethylacetamide, and this solution was poured into a clean glass plate and dried sufficiently in an oven at 80 ° C. to obtain a transparent and flexible film. Can be. The obtained transparent film is as FIG.

Ⅲ. Properties of Poly (N-Monochlorophenylnorbornenedicarboxyimide) Film

Figure 2 shows the results of measuring the thermal stability of the poly (N- monochlorophenyl norbornene dicarboxyimide) polymer film with TGA of TA Instrument, Figure 3 shows the results of measuring the glass transition temperature (T _g ) through DSC It is shown. The thermal properties of this phase are shown in Table 1 below.

T _g (° C) T _d (℃) Poly (N-monochlorophenylnorbornenedicarboxyimide)
226
480

Figure 4 shows the optical properties of the polymer film through a UV-visible spectrometer.

The polymer film according to the present invention exhibits a transmittance of 97% or more in the visible region even after curing at 80 ° C, 160 ° C and 240 ° C.

Figure 5 shows the mechanical properties of the polymer film according to the present invention through a universal testing machine (UTM).

The mechanical properties of this phase are shown in Table 2 below.

σ (Mpa) E (Mpa) ε (Mpa) Poly (N-monochlorophenylnorbornenedicarboxyimide)
63.5 ± 5
2114 ± 175
5.2 ± 0.5

Where σ is tensile strength, E is tensile modulus, and ε is break elongation.

IV. Transparent electrode film formation and organic electroluminescent device fabrication

The polynorbornene dicarboxyimide film in which the N position of the imide was substituted with monochlorophenyl was used as a substrate. Indium tin oxide (ITO), a cathode material, is formed by using magnetron sputtering. Here, zinc oxide (ZnO) may be applied instead of indium tin oxide (ITO).

Subsequently, a hole transport layer, an electron transport layer, and a cathode are sequentially deposited on the indium tin oxide (ITO) film by thermal evaporation to manufacture a flexible organic electroluminescent device.

Although the above has been described with reference to the preferred embodiment of the present invention, various changes can be made at the level of those skilled in the art. For example, in the above embodiment, an organic electroluminescent device was manufactured, but an organic thin film transistor (OTFT) or an organic solar cell having a polynorbornene dicarboxyimide in which the N position of the imide is substituted with a monochlorophenyl group is used as a substrate. organic solar cells).

Accordingly, the scope of the present invention should not be construed as being limited to the embodiments described above, but should be construed in accordance with the following claims.

Claims (11)

N-monochlorophenyl norbornene dicarboxyimide monomer which has a following formula.

Polynorbornene dicarboxyimide having the following formula, wherein the N position of the imide is substituted with a monochlorophenyl group.

Indium tin oxide (ITO) or zinc oxide (ZnO) formed on the transparent film formed by drying the polynorbornene dicarboxyimide of claim 2 as a substrate as a substrate, and sequentially on the indium tin oxide or zinc oxide An organic electroluminescent device comprising a deposited hole transport layer, an electron transport layer, and a cathode. An organic thin film transistor using a transparent film produced by drying the polynorbornene dicarboxyimide of claim 2 as a sheet. An organic solar cell using a transparent peel produced by drying the polynorbornene dicarboxyimide of claim 2 in a sheet form as a substrate. A first step of converting the endo isomer of norbornenedicarboxylic anhydride to the exo isomer of norbornenedicarboxylic anhydride;
A second step of synthesizing norbornenedicarboxylic anhydride of the exo isomer with N-monochlorophenylnorbornenedicarboxyimide; And
A method for producing a polynorbornene dicarboxyimide comprising a monochlorophenyl group comprising a third step of polymerizing the synthesized N-monochloronorbornenedicarboxyimide to synthesize a poly (N-monochlorophenyl norbornenedicarboxyimide). The method of claim 6,
The first step is,
Heating the endo isomer of norbornene dicarboxylic anhydride to 220 ° C. or higher in a nitrogen atmosphere, and then cooling the mixture to 120 ° C .;
At 120 ° C., adding chlorobenzene to the polynorbornenedicarboxylic anhydride to form a mixture;
After cooling the mixture to room temperature, the method of producing a polynorbornene dicarboxyimide comprising a monochlorophenyl group consisting of the step of filtering, washing and drying the crystals. The method of claim 6,
The second step,
Dissolving norbornenedicarboxylic anhydride of the exo isomer in toluene;
Adding and stirring chloroaniline to the norbornenedicarboxylic hydride solution;
Filtering and drying to form amic acid when the suspension is formed while stirring; And
A method for producing a polynorbornene dicarboxyimide comprising a monochlorophenyl group comprising the step of stirring, refluxing the amic acid in anhydrous sodium acetate, acetic anhydride solvent and recrystallized with methanol. The method according to claim 8,
A method for producing a polynorbornene dicarboxyimide comprising a monochlorophenyl group wherein the molar ratio of the amic acid, sodium acetate anhydride, and acetic anhydride is 7: 4:64. The method of claim 6,
In the third step,
Dissolving N-monochlorophenyl norbornenedicarboxyimide in a dichloroethane solvent in a nitrogen atmosphere as a polymerization initiator;
Stopping the reaction by adding ethylvinyl ether in a nitrogen atmosphere;
Precipitating by adding hexane at room temperature;
Dissolving the precipitate in chloroform, hydrochloric acid and then hexane to reprecipitate; And
Method of producing a polynorbornene dicarboxyimide comprising a monochlorophenyl group consisting of drying the re-precipitate. A polynorbornene dicarboxyimide film prepared by the manufacturing method of claim 6 and having transparent and flexible, wherein the N-position of the imide is substituted with a monochlorophenyl group;
Indium tin oxide (ITO) or zinc oxide (ZnO) deposited by sputtering on the film;
An organic electroluminescent device comprising a hole transport layer, an electron transport layer, and a cathode sequentially deposited on the indium tin oxide or zinc oxide.

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