JP5391392B2 - Phenazacillin polymer and organic thin-film transistor using the phenazacillin polymer - Google Patents

Description

  The present invention relates to a polymer having a phenazacillin derivative in the main chain, that is, a novel phenazacillin polymer having a 5,10-dihydro-5H-phenazacillin (hereinafter simply referred to as “phenazacillin”) compound in the main chain, and the phenazacillin-based polymer. The present invention relates to an organic thin film transistor using a polymer.

A phenazacillin compound is known as a compound that prevents oxidation (see, for example, Non-Patent Document 1). It is also known as a heat resistant additive for lubricants in jet engines (see Non-Patent Document 2, for example). Furthermore, it is also known that a low molecular weight compound of phenazacillin is suitably used as a hole transport material for a light emitting device (see, for example, Patent Documents 1 and 2). On the other hand, aromatic amine type polymers such as polyaniline are known to exhibit high electric activity.
Issled. Obl. Fiz. Khim. Kauch. Rezin, 2, 14 (1973) Ann. N. Y. Acad. Sci. , 125, 242 (1965) JP-A-8-302339 Japanese Patent Laid-Open No. 10-218884

  However, when the above-described low molecular weight compounds such as conventional phenazacillin are used as a constituent material of an electronic element such as a light emitting element, film formation is not successful by the casting method, and thus a method such as vacuum deposition is used. In that case, since expensive equipment such as a vacuum vapor deposition apparatus is required, it has been demanded that it can be used as a constituent material of an electronic element by a simpler means. In addition, aromatic amine type polymers such as polyaniline have a problem in that it is difficult to form a film because it is difficult to form a film because of its low solubility in general organic solvents.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a phenazacillin polymer capable of easily and inexpensively producing a homogeneous film and an organic thin film transistor using the phenazacillin polymer. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer having a main chain skeleton of a phenazacillin compound represented by the following general formula (1) has high solubility in an organic solvent. I discovered that it was possible to create a film by the casting method. That is, the polymer of the first invention is characterized in that the main chain skeleton is a phenazacillin compound represented by the following general formula (1).

（式中、Ｒ_３は置換されていてもよい二価のアルキル基を示し、Ｒ_１，Ｒ_２はそれぞれ独立に、置換されていてもよいアルキル基、アリール基、アルコキシ基、アリーロキシ基または水素原子を示し、Ｒ_４は置換されていてもよいアルキル基、アリール基を示す。ｎは平均重合度である。）

(In the formula, R ₃ represents an optionally substituted divalent alkyl group, and R ₁ and R ₂ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group or hydrogen. And R ₄ represents an optionally substituted alkyl group or aryl group, and n is the average degree of polymerization.)

（式中、Ｒ_３は置換されていてもよい二価のアルキル基を示し、Ｒ_１，Ｒ_２はそれぞれ独立に、置換されていてもよいアルキル基、アリール基、アルコキシ基、アリーロキシ基または水素原子を示し、ｎは平均重合度である。） The polymer of the second invention is characterized by having a phenazacillin compound represented by the following general formula (2) as a main chain skeleton.

(In the formula, R ₃ represents an optionally substituted divalent alkyl group, and R ₁ and R ₂ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group or hydrogen. Represents an atom, and n is the average degree of polymerization.)

（式中、Ｒ_１，Ｒ_２はそれぞれ独立に、置換されていてもよいアルキル基、アリール基、アルコキシ基、アリーロキシ基または水素原子を示し、ｎは平均重合度である。） The polymer of the third invention is characterized by having a phenazacillin compound represented by the following general formula (3) as a main chain skeleton.

(In the formula, R ₁ and R ₂ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group or hydrogen atom, and n is the average degree of polymerization.)

（式中、Ｒ_１，Ｒ_２，Ｒ_５はそれぞれ独立に置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアルコキシ基、置換されていてもよいアリーロキシ基または水素原子を示す。） Furthermore, according to this invention, an organic transistor is provided by using the polymer as described in General formula (4) containing the polymer of General formula (1)-(3) for a thin film.

(Wherein R ₁ , R ₂ and R ₅ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy; Represents a group or a hydrogen atom.)

In the general formulas (1) to (4), the alkyl group represented by R ₁ , R ₂ , R ₄ , R ₅ is methyl, ethyl, n- or iso-propyl, n-, iso- or tert. A linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms such as -butyl, n-, iso- or neo-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, etc. Can be mentioned. Examples of the aryl group include phenyl groups, o-, m-, p-tolyl groups, 1- and 2-naphthyl groups, anthryl groups, fluorenyl groups and the like, and aryl groups having 6 to 50 carbon atoms, preferably 6 to 32 carbon atoms. It is done.

In the general formulas (1) to (4), examples of the alkoxy group represented by R ₁ , R ₂ , R ₅ include methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, Examples thereof include linear, branched and cyclic alkoxy groups having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms such as n-, iso- or neo-pentoxy, n-hexoxy, cyclohexoxy, n-heptoxy and n-octoxy. . Examples of the aryloxy group include aryloxy groups having 6 to 50 carbon atoms, preferably 6 to 32 carbon atoms such as phenoxy group, o-, m-, p-triloxy group, 1- and 2-naphthoxy group, anthoxy group and fluorenyl group. It is done.

Examples of the divalent alkyl group represented by R ₃ include methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, Examples thereof include a linear or branched divalent alkyl group having 1 to 20, preferably 2 to 8, carbon atoms such as propane-1,3-diyl.

  The average degree of polymerization n in the general formulas (1) to (4) can take any number exceeding 1, but is preferably in the range of 2 <n <10000.

  Since the phenazacillin polymer of the present invention is easily dissolved in a normal organic solvent such as halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, organic acids such as trifluoroacetic acid, toluene and THF without crystallization, A thin film can be formed by simply forming a film using a normal coating method such as a spin coating method, a dip coating method, or a roll coating method, and can be used as a constituent material of an organic thin film transistor.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples.

Example 1
Synthesis of poly (5,10-dimethyl-10- {2-[(9H-fluoren-2-yl) iminocarbonyloxy] ethyl} -5,10-dihydrophenazacillin-2,8-diyl) (general formula (1), R ₁ = R ₂ = methyl group, R ₃ = ethane-1,2-diyl, R ₄ = fluorenyl group)

  First, 5.07 g of N-methyl-2,2 ′, 4,4′-tetrabromodiphenylamine was suspended in 80 mL of ether in an ice bath, and then 13.0 mL of n-butyllithium in hexane solution (1 .6M) was added. Further, 1.43 g of dichloromethylvinylsilane was added, and after the precipitate was formed, the ice bath was removed and the mixture was stirred for 24 hours. The reaction solution was poured into ice water, extracted with ether and then washed with hexane to obtain 2.86 g of 2,8-dibromo-5,10-dimethyl-10-vinyl-5,10-dihydrophenazacillin as a white powder. Isolated.

  Subsequently, 660 mg of 9-BBN dimer was added to a solution of 400 mg of 2,8-dibromo-5,10-dimethyl-10-vinyl-5,10-dihydrophenazacillin in 10 mL of THF for 3 days. Stir. Further, 5 mL of 34.5% hydrogen peroxide solution and 7 mL of 3N aqueous sodium hydroxide solution were added and stirred for one day. The product was extracted with ethyl acetate and the silica gel column purified was further washed with hexane to give 314 mg of 2,8-dibromo-5,10-dimethyl-10- (2-hydroxyethyl) -5, 10-dihydrophenazacillin was obtained.

  Further, 9H-fluorene-2- (2,8-dibromo-5,10-dimethyl-10- (2-hydroxyethyl) -5,10-dihydrophenazacillin in a solution of 0.44 g in 10 mL of toluene was added. 0.22 g of yl isocyanate was added and stirred at 100 ° C. The precipitate obtained by pouring the reaction solution into hexane was filtered to obtain 2,8-dibromo-5,10-dimethyl-10- {2-[(9H-fluoren-2-yl) iminocarbonyloxy as a yellow powder. ] 0.56 g of ethyl} -5,10-dihydrophenazacillin was isolated.

  Further, 1 mL of 1,5-cyclooctadiene was added to 320 mg of bis (cyclooctadiene) nickel (0) under a nitrogen atmosphere, and then 5 mL of toluene was added to suspend the mixture. Further, 190 mg of 2,2'-bipyridyl was added and stirred. Further 484 mg (0.76 mmol) 2,8-dibromo-5,10-dimethyl-10- {2-[(9H-fluoren-2-yl) iminocarbonyloxy] ethyl} -5,10-dihydrophenazacillin The mixture was heated to 60 ° C. and stirred for 48 hours. The reaction solution was poured into methanol, and the precipitated powder was washed with water and then with methanol. Further, 315 mg (0.66 mmol as a monomer unit) of the polymer (polymer 1) was isolated by dissolving the powder in chloroform and reprecipitating with hexane.

The obtained polymer 1 had a number average molecular weight of 4200 (n = 8.9) and a weight average molecular weight of 8200 (n = 17.3), which was a sufficient degree of polymerization for producing a cast film. This substance was identified by IR and ¹ H-NMR spectrum.

窒素雰囲気下で２８０ｍｇのビス（シクロオクタジエン）ニッケル（０）に１，５−シクロオクタジエン１ｍＬを加えた後にトルエン１０ｍＬを加えて懸濁させた。さらに２，２’−ビピリジル１６０ｍｇを加えて攪拌した。さらに１９１ｍｇ（０．３８ｍｍｏｌ）の２，８−ジブロモ−５，１０−ジメチル−１０−ビニル−５，１０−ジヒドロフェナザシリンを加えた後に６０℃に昇温して４８時間攪拌した。反応液に水を加え、さらにクロロホルムで抽出した後、有機層の溶媒を留去させることにより上記化合物（ポリマー２）を１３８ｍｇ（モノマーユニットとして０．１２ｍｍｏｌ）を単離した。 Example 2
Synthesis of poly (5,10-dimethyl-10-vinyl-5,10-dihydrophenazacillin-2,8-diyl) shown below (general formula (3), R ₁ = R ₂ = methyl group)

Under a nitrogen atmosphere, 1 mL of 1,5-cyclooctadiene was added to 280 mg of bis (cyclooctadiene) nickel (0), and then 10 mL of toluene was added and suspended. Further, 160 mg of 2,2′-bipyridyl was added and stirred. Further, 191 mg (0.38 mmol) of 2,8-dibromo-5,10-dimethyl-10-vinyl-5,10-dihydrophenazacillin was added, and the mixture was heated to 60 ° C. and stirred for 48 hours. After adding water to the reaction solution and further extracting with chloroform, 138 mg (0.12 mmol as a monomer unit) of the above compound (polymer 2) was isolated by distilling off the solvent of the organic layer.

The number average molecular weight of the chloroform soluble part of the polymer 2 was 1300 (n = 5.2), and the weight average molecular weight was 1900 (n = 7.6). This substance was identified by IR and ¹ H-NMR spectrum.

窒素雰囲気下、ポリ（５，１０−ジメチル−１０−ビニル−５，１０−ジヒドロフェナザシリン−２，８−ジイル）５３．９ｍｇを５ｍＬのＴＨＦに分散させ、続いて０．１６ｇの９−ＢＢＮダイマーを加えて１日攪拌した。さらに、５ｍＬの３４．５％過酸化水素水、７ｍＬの３Ｎ水酸化ナトリウム水溶液を加えて一日攪拌した。反応液を水に注いで析出した粉末を、２Ｍ塩酸、次いで水で洗浄することにより、４３．４ｍｇのポリ（５，１０−ジメチル−１０−（２−ヒドロキシエチル）−５，１０−ジヒドロフェナザシリン−２，８−ジイル）を単離した。 Example 3
Synthesis of poly (5,10-dimethyl-10- (2-hydroxymethyl) -5,10-dihydrophenazacillin-2,8-diyl) shown below (general formula 2, R ₃ = ethane-1,2 -Diyl, R ₁ = R ₂ = methyl group)

Under a nitrogen atmosphere, 53.9 mg of poly (5,10-dimethyl-10-vinyl-5,10-dihydrophenazacillin-2,8-diyl) was dispersed in 5 mL of THF followed by 0.16 g of 9- BBN dimer was added and stirred for 1 day. Further, 5 mL of 34.5% hydrogen peroxide solution and 7 mL of 3N aqueous sodium hydroxide solution were added and stirred for one day. The reaction solution was poured into water, and the precipitated powder was washed with 2M hydrochloric acid and then with water to obtain 43.4 mg of poly (5,10-dimethyl-10- (2-hydroxyethyl) -5,10-dihydrophena. Zacillin-2,8-diyl) was isolated.

Example 4
1 is a schematic cross-sectional view of an organic thin film transistor 10. As shown in FIG. A glass plate having a thickness of 0.7 mm was used as the substrate 6, and this glass plate was subjected to ultrasonic cleaning using ultrapure water and an organic solvent, and then aluminum was vacuum-deposited as the gate electrode 5 by 50 nm.

  Next, after ozone cleaning, a polyimide precursor film was formed on the gate electrode 5 by spin coating, and baked at 200 ° C. to form a gate insulating layer 4 having a thickness of 270 nm. Thereafter, a resist was formed on the gate electrode 5 using back exposure, and gold was deposited thereon by 50 nm vacuum vapor deposition, followed by lift-off to form the source electrode 2 and the drain electrode 3. From this, a 1.5 wt% toluene solution of polyphenazacillin was formed into a polymer layer by spin coating to produce an organic thin film transistor 10.

Poly (10,10-dioctyl-5-methylphenazacillin) (general formula (4), R ₁ = R ₅ = octyl group, R ₂ = methyl group) is used as polyphenazacillin, gate length is 193 μm, gate width fabricated elements in 688Myuemu, mobility ^{2.14 × 10- 4 [cm 2 /} Vs], on-off ratio of ¹⁰ 3. ¹⁰ and p-type transistor characteristics with a threshold voltage of −25.5 V were exhibited.

Example 5
As a polymer in the device prepared by the method described in Example 4, polymer 1 (general formula (4), R ₁ = R ₂ = methyl group, R ₅ = 2-[(9H-fluoren-2-yl)) imino used carbonyloxy] ethyl group), a gate length 50 [mu] m, the element fabricated by the gate width 700 .mu.m, mobility ^{3.38 × 10- 7 [cm 2 /} Vs], on-off ratio ¹⁰ 1. ⁰⁹ , p-type transistor characteristics with a threshold voltage of −9.83 V were shown.

1 is a schematic cross-sectional view of an organic thin film transistor element 10. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyphenazacillin 2 Source electrode 3 Drain electrode 4 Gate insulating layer 5 Gate electrode 6 Substrate

Claims (4)

A phenazacillin polymer having a main chain skeleton of a 5,10-dihydro-5H-phenazacillin compound represented by the following general formula (1).

(In the formula, R ₃ represents an optionally substituted divalent alkyl group, and R ₁ , R ₂ and R ₄ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group. A group or a hydrogen atom, and n is the average degree of polymerization.) A phenazacillin polymer having a main chain skeleton of a 5,10-dihydro-5H-phenazacillin compound represented by the following general formula (2).

(In the formula, R ₃ represents an optionally substituted divalent alkyl group, and R ₁ and R ₂ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group or hydrogen. Represents an atom, and n is the average degree of polymerization.) A phenazacillin polymer having a main chain skeleton of a 5,10-dihydro-5H-phenazacillin compound represented by the following general formula (3).

(In the formula, R ₁ and R ₂ each independently represents an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group or hydrogen atom, and n is the average degree of polymerization.) An organic thin film transistor using a phenazacillin polymer represented by the following general formula (4).

(Wherein R ₁ , R ₂ and R ₅ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy; Represents a group or a hydrogen atom.)

Images