JP2018177842A - MANUFACTURING METHOD OF FLUORINE-CONTAINING π-CONJUGATED CYCLIC POLYMER, AND LIGHT EMITTING ELEMENT USING THE FLUORINE-CONTAINING π-CONJUGATED CYCLIC POLYMER OBTAINED BY THE MANUFACTURING METHOD - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a fluorine-containing π-conjugated cyclic polymer high in solubility in an organic solvent and good in deposition property while achieving π electron conjugation property sufficiently, and excellent in stability and durability, and the fluorine-containing π-conjugated cyclic polymer obtained by the manufacturing method, and a light emitting element using the same.SOLUTION: There is provided a manufacturing method of a fluorine-containing π-conjugated cyclic polymer manufactured by conducting single polymerization or copolymerization of a fluorine-containing π-conjugated cyclic polymer precursor monomer by a homo or cross coupling reaction using a transition metal catalyst, the fluorine-containing π-conjugated cyclic polymer precursor monomer is synthesized by a reaction of a single cyclic or chain-shaped compound (A) having one of a double bond and one or more fluorine element in a molecule and a compound (B), which is a π-conjugated cyclic compound and has 2 or 4 hydroxyl groups at an ortho position and a bromine atom, a chlorine atom or an iodine atom at a para position as a nucleus substitution group.SELECTED DRAWING: Figure 1

Description

  The present invention provides a method for producing a fluorine-containing π-conjugated cyclic polymer having high solubility in an organic solvent and good film forming properties while sufficiently exhibiting π electron conjugation, and excellent in stability and durability. The present invention relates to a light emitting device using the fluorine-containing π-conjugated cyclic polymer obtained by the production method.

  A π-conjugated compound having a π-conjugated double bond in its main chain exhibits conductivity and light absorption and emission characteristics in the visible light region, and is used for display element materials such as organic EL (electroluminescence), recording materials or field effect transistors It has been actively studied to use it for solar cells and the like. As π-conjugated compounds, oligomers and polymers having a basic skeleton such as acetylene, thiophene, phenylene, phenylenevinylene and the like are conventionally known. For example, Non-Patent Document 1 describes structure control synthesis of π-conjugated polymers The law is described. In addition to these skeletons, oligomers such as pentacene and polymers having a basic skeleton such as fluorene and phenanthrolene have also been studied.

  When the π-conjugated compound is applied as an organic semiconductor, materials having semiconductor characteristics of p-type or n-type are selected and used according to the device and application. For example, both p-type and n-type materials are used in EL elements and solar cells. Pentacene, thiophene and the like are known as p-type semiconductor materials, and many candidate materials have been studied conventionally. On the other hand, although n-type semiconductor materials have few kinds of materials in the first place and a small number of n-type organic semiconductors such as fluorine-containing compounds of pentafluoropentacene and fullerenes are known, materials applicable specifically are extremely The current situation is limited. Therefore, development of a new n-type organic semiconductor material is strongly required to expand the scope of application in the future. Among n-type organic semiconductor compounds, π-conjugated polymers, in particular, have film-forming properties and processability that are unique to polymers, and can be expected to be applied to various fields, so there is a demand for development of new polymer materials Is very expensive.

  There is also a method of newly synthesizing a compound having a special structure such as fullerene etc. for the synthesis of the n-type semiconductor polymer, but by introducing a fluorine skeleton into an existing p-type organic semiconductor compound, the n-type organic semiconductor The method of conversion is very effective in that the range of choice of materials can be expanded. Based on such a viewpoint, Patent Document 1 proposes a condensation compound of a fluorinated cyclopentanone ring and an aromatic ring useful for an electronic material and a method for producing the same.

  The present inventors also propose a phenanthroline compound having a fluorine skeleton (see Patent Document 2) and a polymer having a fused polycyclic aromatic skeleton (see Patent Document 3) as a compound having a fluorine skeleton introduced in the molecule. did. Polymers having these compounds or their skeletons are characterized by having higher solubility in organic solvents and superior stability and durability as compared to π-conjugated compounds having no fluorine skeleton or their polymers. It is.

Unexamined-Japanese-Patent No. 2006-248944 JP, 2016-60772, A JP, 2016-84448, A

Wakioka Masayuki, Takita Ryo, Ozawa Fumiyuki, "Structure-Controlled Synthesis of π-Conjugated Polymers by Transition Metal Catalyst", Journal of Japan Rubber Association, 2008, Vol. 81, No. 10, pp. 431-437

  In order to expand the application as a n-type semiconductor by using a π-conjugated polymer having a fluorine skeleton introduced, it is possible not only to improve the characteristics as an n-type semiconductor, but also to have high heat resistance and high durability and It is more and more necessary to improve film formability and processability by enhancing the solubility in a solvent. Furthermore, since it is essential to reduce the material cost of the π-conjugated polymer having a fluorine skeleton introduced, there is a need for a synthesis method which is easy to obtain raw materials, has a small number of synthetic steps, and can increase the yield if possible.

  However, the synthesis method described in Patent Document 1 involves many reaction steps when synthesizing a condensation compound of a fluorinated cyclopentanone ring and an aromatic ring, which are polymer precursors, and in some cases, special raw materials. Need to use. Therefore, when the condensation compound is used as a raw material to perform oligomerization or polymerization, the cost of production and materials tends to be high. Furthermore, the fused compound of a fluorinated cyclopentanone ring and an aromatic ring has a basic cyclic structure of two rings of a cyclopentanone ring and an aromatic ring, so that the heat resistance, durability, and general organic solvent are obtained. Improvements are still needed in terms of solubility.

  Further, the phenanthroline compound having a fluorine skeleton described in Patent Document 2 and the polymer having a fused polycyclic aromatic skeleton described in Patent Document 3 are generally used because the basic skeleton is a polycyclic aromatic group. A novel π-conjugated system having a basic skeleton different from that of the above-mentioned polycyclic aromatics in order to further improve the solubility in organic solvents, impart flexibility of a thin film formed after film formation, and expand the range of material selection. Development of polymeric materials is strongly desired.

  The present invention has been made in view of the above-described conventional problems, and has high solubility in an organic solvent and good film formability while sufficiently exhibiting π electron conjugation, and stability and Method for producing a fluorine-containing π-conjugated cyclic polymer that is excellent in durability, easy to obtain raw materials in synthesis, and can be synthesized with a smaller number of steps than conventional, and a fluorine-containing π-conjugated system obtained by the method The present invention relates to a light emitting element using a cyclic polymer.

  The present invention is a fluorine-containing π-conjugated cyclic polymer precursor in which at least one hydrogen is substituted with a fluorine atom to introduce two or one of saturated hydrocarbon structures of a hydrocarbon-based saturated cyclic structure into a monocyclic aromatic ring. A monomer is synthesized, and the fluorine-containing π-conjugated cyclic polymer precursor monomer is homopolymerized or copolymerized with another π-conjugated polymer precursor monomer by homocoupling reaction or cross coupling reaction. The present invention has been found out that the problems of the invention can be solved.

式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子であり、Ｒ_５１、Ｒ_６１、は、それぞれ独立にフッ素原子、臭素原子又は塩素原子である。ａ、ｂ、ｃ、ｄは０又は１の整数であり、ａ＋ｂ＋ｃ＋ｄ＝２〜４の何れかの整数である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４において、Ｒ_１及び該Ｒ_１とシス位の置換基であるＲ_３は、フッ素原子、臭素原子又は塩素原子であり、Ｒ_２、Ｒ_４はフッ素原子又はフッ素原子を１個以上含むアルキル基である。

式中、Ｘ_１、Ｘ_２は、独立に臭素原子、塩素原子又はヨウ素原子であり、Ｒ_ａ、Ｒ_ｂは、独立に水素原子、アルキル基又はアリール基である。Ｙは、下記（Ｙ１）〜（Ｙ９）のいずれかで表される原子又は原子団であり、

式中、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆは、それぞれ独立に水素原子又は置換基である。
［３］本発明は、前記Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２、Ｒ_５１、Ｒ_６１、Ｒ_１、Ｒ_３が、何れもフッ素原子であり、前記Ｒ_２、Ｒ_４が、独立にフッ素原子又はパーフルオロアルキル基であることを特徴とする前記［２］に記載の含フッ素π共役系環状高分子の製造方法を提供する。
［４］本発明は、前記ａ＋ｂ＋ｃ＋ｄがａ＋ｂ＋ｃ＋ｄ＝３の整数であることを特徴とする前記［２］又は［３］に記載の含フッ素π共役系環状高分子の製造方法を提供する。
［５］本発明は、前記Ｘ_１及びＸ_２が、臭素原子であることを特徴とする前記［２］〜［４］のいずれか一項に記載の含フッ素π共役系環状高分子の製造方法を提供する。
［６］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（１）で表される化合物と、前記式（３）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（６）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法。

式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子である。
［７］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（１）で表される化合物と、前記式（４）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（７）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子である。Ｒ_ａ、Ｒ_ｂは、独立に水素原子、アルキル基又はアリール基である。
［８］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（１）で表される化合物と、前記式（５）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（８）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子である。Ｙは、前記（Ｙ１）〜（Ｙ９）のいずれかで表される原子又は原子団と同じ原子又は原子団である。
［９］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（２）で表される化合物と、前記式（３）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（９）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_２、Ｒ_４はフッ素原子又はフッ素原子を１個以上含むアルキル基である。
［１０］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（２）で表される化合物と、前記式（４）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（１０）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_２、Ｒ_４はフッ素原子又はフッ素原子を１個以上含むアルキル基であり、Ｒ_ａ、Ｒ_ｂは、独立に水素原子、アルキル基又はアリール基である。
［１１］本発明は、前記［２］〜［５］のいずれか一項に記載の製造方法において、前記式（２）で表される化合物と、前記式（５）で表される化合物とから合成される含フッ素π共役系環状高分子前駆体モノマを用いて、下記式（１１）で表される構造単位を有する含フッ素π共役系環状高分子を製造することを特徴とする含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_２、Ｒ_４はフッ素原子又はフッ素原子を１個以上含むアルキル基である。Ｙは、前記（Ｙ１）〜（Ｙ９）のいずれかで表される原子又は原子団と同じ原子又は原子団である。
［１２］前記含フッ素π共役系環状高分子前駆体モノマを、前記含フッ素π共役系環状高分子前駆体モノマとは別のπ共役系高分子前駆体モノマとクロスカップリング反応させることにより、さらに、下記式（１２）、（１３）、（１４）及び（１５）で表される構造単位の少なくともいずれかを有する共重合体を製造することを特徴とする前記［６］〜［１１］のいずれか一項に記載の含フッ素π共役系環状高分子の製造方法を提供する。

式中、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０は、それぞれ独立に水素原子、アルキル基又はアルコキシ基を示し、ｅ、ｇ、ｈは１〜４のいずれかの整数で、ｆは１〜２のいずれかの整数である。Ｚは、下記（Ｚ１）〜（Ｚ９）のいずれかで表される原子又は原子団であり、

式中、Ｒｇ、Ｒｈ、Ｒｉ、Ｒｊは、それぞれ独立に水素原子又は置換基である。
［１３］本発明は、前記共重合体が、前記含フッ素π共役系環状高分子前駆体モノマの重合によって前記フッ素π共役系環状高分子中に形成される構造単位と、前記式（１２）、（１３）、（１４）及び（１５）で表される構造単位のいずれかとが交互に化学結合した交互共重合体であることを特徴とする前記［１２］に記載の含フッ素π共役系環状高分子の製造方法を提供する。
［１４］本発明は、前記［１］〜［１３］のいずれか一項に記載の製造方法で製造された含フッ素π共役系環状高分子を発光層の発光材料として含む発光素子を提供する。 That is, the constitution of the present invention is as follows.
[1] The present invention relates to a fluorine-containing π-conjugated system produced by homopolymerization or copolymerization of a fluorine-containing π-conjugated cyclic polymer precursor monomer by homo-coupling reaction or cross-coupling reaction using transition metal catalyst A method for producing a cyclic polymer, wherein the fluorine-containing π-conjugated cyclic polymer precursor monomer is a monocyclic or chain compound having one of double bond and one or more of fluorine element in one molecule. (A) and a cyclic compound of π conjugated system, and a compound (B) having 2 or 4 hydroxyl groups at the ortho position and a bromine atom, a chlorine atom or an iodine atom at the para position as a nuclear substituent Disclosed is a method for producing a fluorine-containing π-conjugated cyclic polymer characterized by being synthesized by a reaction.
[2] The present invention is a compound having a structure in which the compound (A) is represented by the following formula (1) or (2), and the compound (B) is a compound represented by the following formula (3), (4) or It is a compound which has a structure represented by 5), The manufacturing method of the fluorine-containing pi conjugated cyclic polymer as described in said [1] characterized by the above-mentioned is provided.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom, and R ₅₁ and R ₆₁ each independently represent a fluorine atom, a bromine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and a + b + c + d is an integer in any one of 2 to 4. In R ₁ , R ₂ , R ₃ and R ₄ , R ₁ and R ₃ which is a substituent in the cis position with R ₁ are a fluorine atom, a bromine atom or a chlorine atom, and R ₂ and R ₄ are a fluorine atom Or an alkyl group containing one or more fluorine atoms.

In the formula, X ₁ and X _{2 each} independently represent a bromine atom, a chlorine atom or an iodine atom, and R _a and R _{b each} independently represent a hydrogen atom, an alkyl group or an aryl group. Y is an atom or atomic group represented by any of the following (Y1) to (Y9),

In the formula, Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent.
[3] In the present invention, each of R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₅₁ , R ₆₁ , R ₁ and R ₃ is a fluorine atom. The method for producing a fluorine-containing π-conjugated cyclic polymer according to the above [2], wherein R ₂ and R ₄ are independently a fluorine atom or a perfluoroalkyl group.
[4] The present invention provides the method for producing a fluorine-containing π-conjugated cyclic polymer according to the above [2] or [3], wherein the a + b + c + d is an integer of a + b + c + d = 3.
[5] The present invention is the production of the fluorine-containing π-conjugated cyclic polymer according to any one of the above [2] to [4], wherein X ₁ and X ₂ are a bromine atom. Provide a way.
[6] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (1) and the compound represented by the formula (3) Wherein a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (6) is produced using a fluorine-containing π-conjugated cyclic polymer precursor monomer synthesized from Method for producing π-conjugated cyclic polymer

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom.
[7] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (1) and the compound represented by the formula (4) A fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (7) using a fluorine-containing π-conjugated cyclic polymer precursor monomer synthesized from Provided is a method for producing a π-conjugated cyclic polymer.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. R _a and R _b are independently a hydrogen atom, an alkyl group or an aryl group.
[8] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (1) and the compound represented by the formula (5) A fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (8) using a fluorine-containing π-conjugated cyclic polymer precursor monomer synthesized from Provided is a method for producing a π-conjugated cyclic polymer.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. Y is the same atom or atomic group as the atom or atomic group represented by any one of (Y1) to (Y9) above.
[9] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (2) and the compound represented by the formula (3) A fluorine-containing pi-conjugated cyclic polymer having a structural unit represented by the following formula (9) using a fluorine-containing pi-conjugated cyclic polymer precursor monomer synthesized from Provided is a method for producing a π-conjugated cyclic polymer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms.
[10] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (2) and the compound represented by the formula (4) Wherein a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (10) is produced using a fluorine-containing π-conjugated cyclic polymer precursor monomer synthesized from Provided is a method for producing a π-conjugated cyclic polymer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms, and R _a and R _{b each} independently represent a hydrogen atom, an alkyl group or an aryl group.
[11] The present invention provides the method according to any one of the above [2] to [5], wherein the compound represented by the formula (2) and the compound represented by the formula (5) A fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (11) using a fluorine-containing π-conjugated cyclic polymer precursor monomer synthesized from Provided is a method for producing a π-conjugated cyclic polymer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms. Y is the same atom or atomic group as the atom or atomic group represented by any one of (Y1) to (Y9) above.
[12] A cross coupling reaction of the fluorine-containing π-conjugated cyclic polymer precursor monomer with a π-conjugated polymer precursor monomer different from the fluorine-containing π-conjugated cyclic polymer precursor monomer Furthermore, a copolymer having at least one of the structural units represented by the following formulas (12), (13), (14) and (15) is produced, and the above-mentioned [6] to [11] The method for producing a fluorine-containing π-conjugated cyclic polymer according to any one of the above.

In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and e, g, h are integers of 1 to 4 and f is 1 to Any integer of 2. Z is an atom or atomic group represented by any of the following (Z1) to (Z9),

In the formula, Rg, Rh, Ri and Rj are each independently a hydrogen atom or a substituent.
[13] The present invention provides a structural unit in which the copolymer is formed in the fluorine π-conjugated cyclic polymer by polymerization of the fluorine-containing π-conjugated cyclic polymer precursor monomer, and the formula (12) And (13), (14), and (15), which is an alternating copolymer in which any of the structural units represented by (12), (14) and (15) are chemically bonded alternately. Provided is a method of producing a cyclic polymer.
[14] The present invention provides a light emitting device comprising the fluorine-containing π-conjugated cyclic polymer produced by the method according to any one of the above [1] to [13] as a light emitting material of a light emitting layer. .

  According to the method for producing a fluorine-containing π-conjugated cyclic polymer of the present invention, two or one of the saturated cyclic structures of a hydrocarbon system in which at least one hydrogen is substituted by a fluorine atom in a monocyclic aromatic ring. A fluorine-containing π-conjugated cyclic polymer precursor monomer into which one is introduced and a fluorine-containing π-conjugated cyclic polymer obtained by polymerizing the precursor monomer by homopolymerization or copolymerization, using easily available raw materials, It can be obtained with a smaller number of synthetic steps than before.

  In addition, the fluorine-containing π-conjugated cyclic polymer obtained by the production method of the present invention has high solubility in an organic solvent and good film-forming properties, while sufficiently exhibiting π electron conjugation. Excellent in durability. Furthermore, by applying the fluorine-containing π-conjugated cyclic polymer of the present invention to an electronic material as an n-type organic semiconductor, it is possible to solve the conventional technical problems that the number of types of n-type semiconductor materials is small. It can be expected to apply to electronic devices and solar cells having functions. For example, a light emitting element having the fluorine-containing π-conjugated cyclic polymer of the present invention as a light emitting material can not only enhance the light emission performance but also improve the durability.

FIG. 2 is a schematic view of a synthesis reaction for producing the fluorine-containing π-conjugated cyclic polymer of the present invention. It is a schematic diagram of another synthetic reaction for manufacturing the fluorine-containing pi conjugated cyclic polymer of the present invention. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (13), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (14), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows another example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (12), and another example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows another example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (12), and another example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows another example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (6) and Formula (14), and another example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (7) and Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows another example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (9) and Formula (12), and another example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (10) and Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (8) and Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method. It is a figure which shows the example of the manufacturing method of the alternating copolymer which has a structural unit represented by Formula (11) and Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method. FIG. 2 is a view showing a crystal structure estimated by X-ray crystal structure analysis of the fluorine-containing π-conjugated polymer precursor monomer 1 synthesized in Example 1.

  The process for producing a fluorine-containing π-conjugated cyclic polymer according to the present invention comprises homopolymerizing another fluorine-containing π-conjugated cyclic polymer precursor monomer or another π-conjugated by homo-coupling reaction or cross-coupling reaction using a transition metal catalyst. A method for producing a fluorine-containing π-conjugated cyclic polymer produced by copolymerization with a high-molecular-weight polymer precursor monomer, wherein the fluorine-containing π-conjugated cyclic polymer precursor monomer has a double bond. A single cyclic or chain compound (A) having one or more of the fluorine elements in one molecule, and a cyclic compound of π conjugated system, and two or four ortho substituents as a nuclear substituent The compound is synthesized by the reaction with a compound (B) having a bromine atom, a chlorine atom or an iodine atom at the hydroxyl group and the para position of As described above, the present invention is characterized in that it is a novel compound having a structure in which the above-mentioned fluorine-containing π-conjugated cyclic polymer precursor monomer is not present in the prior art.

  The precursor monomer has a chemical structure which introduces, into a monocyclic aromatic ring, two or one of a hydrocarbon-based saturated cyclic structure in which at least one of hydrogens is substituted with a fluorine atom, and has low toxicity. In addition, it is characterized in that it is synthesized by performing a dehydrohalogenation reaction under mild conditions (below room temperature) using raw materials which are commercially available and easy to handle. Therefore, the synthesis route can be shortened and introduced basically by a one-step reaction process, and even if the reaction of oligomerization or polymerization of the precursor monomer is added, the reaction process is two steps and the reaction is less The fluorine-containing π-conjugated cyclic polymer of the present invention can be produced at the process stage.

  Thus, since the fluorine-containing π-conjugated cyclic polymer obtained by the production method of the present invention constitutes a molecular main chain having a monocyclic aromatic ring as a basic skeleton, it originally has high π-conjugated properties. In addition, since a hydrocarbon-based saturated cyclic structure in which at least one hydrogen is substituted with a fluorine atom is bonded to the monocyclic aromatic ring at a position corresponding to a side chain, a repeating unit of the polymer The constituting basic skeleton tends to form a three-dimensional planar structure. As a result, since the fluorine-containing π-conjugated cyclic polymer of the present invention has a basic skeleton that can be easily stacked in a stack, it is possible to further enhance the π-conjugated property.

  On the other hand, the saturated cyclic structure of the hydrocarbon group has no π conjugation in the direction perpendicular to the polymer main chain, and has a bulky structure, and thus has the effect of significantly enhancing the solubility in a common organic solvent. can get. Furthermore, this saturated cyclic structure greatly contributes to the improvement of the heat resistance and the durability as compared with the chain substituent. Therefore, unlike the conventional method of introducing a chain substituent or the like in order to improve the solubility in organic solvents, the deterioration of physical properties and characteristics required for light emitting materials of EL elements and electronic materials such as organic solar cells It is excellent in the point which hardly invites. And according to the present invention, depending on the solubility in organic solvents, the film formation of organic thin films, the heat resistance and the durability, one or two of the above-mentioned hydrocarbon saturated ring structures may be used as a polymer repeating unit. It can be introduced into a monocyclic aromatic ring polymer which is a basic skeleton.

  Here, the hydrocarbon-based saturated cyclic structure has a large atomic radius and introduces electron-withdrawing strong fluorine atoms or chlorine atoms instead of hydrogen atoms to impart heat resistance and form a polymer main chain. Further effect can be obtained on the electron withdrawing property of the monocyclic aromatic ring skeleton and on the solubility in common organic solvents.

  As described above, the fluorine-containing π-conjugated cyclic polymer obtained by the production method of the present invention has high solubility in an organic solvent and good film-forming property, while sufficiently exhibiting π electron conjugation. Excellent in durability and durability. Furthermore, since the fluorine-containing π-conjugated cyclic polymer having various structures can be produced according to these physical properties and properties, the application range can be greatly expanded when applied as an electronic material.

  Hereinafter, the method for producing a fluorine-containing π-conjugated cyclic polymer of the present invention will be described in detail. FIGS. 1 and 2 schematically show a method of producing the fluorine-containing π-conjugated cyclic polymer of the present invention.

  FIG. 1 is a view schematically showing a method for producing the fluorine-containing π-conjugated polymer of the present invention having a structural unit represented by the above formula (6), (7) or (8), and A fluorine-containing π-conjugated cyclic high is obtained by reacting a fluorine-containing cycloalkene compound having a structure represented by 1) with a compound having a structure represented by the formula (3), (4) or (5). After synthesizing molecular precursor monomers (compounds represented by formulas (13M), (14M) and (15M) in the figure), these fluorine-containing π-conjugated cyclic polymer precursor monomers are known using transition metal catalysts. The polymerization is carried out by homocoupling reaction to produce. Moreover, FIG. 2 is a figure which shows typically the manufacturing method of the fluorine-containing pi conjugated polymer of this invention which has a structural unit represented by said Formula (9), (10) or (11), and said Fluorine-containing π-conjugated cyclic ring by reacting a fluorine-containing alkene compound having a structure represented by formula (2) with a compound having a structure represented by formula (3), (4) or (5) After synthesizing a polymer precursor monomer (compounds represented by formulas (23M), (24M) and (25M) in the figure), these fluorine-containing π-conjugated cyclic polymer precursor monomers are known using a transition metal catalyst The polymerization is carried out by the homocoupling reaction of In addition, when manufacturing the below-mentioned copolymer as a fluorine-containing pi conjugated cyclic polymer of this invention, it replaces with the said homo coupling reaction, and performs copolymerization by the cross coupling reaction.

<Method of producing fluorine-containing π-conjugated cyclic polymer precursor monomer>
The fluorine-containing π-conjugated cyclic polymer precursor monomer used in the present invention is a monocyclic or chain compound (A) having one of double bonds and one or more of fluorine elements in one molecule; It is synthesized by the reaction with a compound (B) which is a conjugated cyclic compound and which has, as a nuclear substituent, 2 or 4 hydroxyl groups in the ortho position and a bromine atom, chlorine atom or iodine atom in the para position. The schematic diagrams of their synthesis methods are shown together with FIGS. 1 and 2.

  As shown in FIG. 1, the fluorine-containing π-conjugated cyclic polymer precursor monomer [compounds represented by (13M), (14M), (15M) in the figure] used in the present invention is the compound (A) For example, a compound having a structure represented by the following formula (1) to be used and a compound having a structure represented by the following formula (3), (4) or (5) used as the compound (B), for example, Dissolved in an aprotic polar organic solvent such as dimethyl sulfone oxide (DMSO), dimethylformamide (DMF), diethyl ether, tetrahydrofuran etc., alkali metal salts such as potassium carbonate, alkali metal salts of phosphoric acid, alkali metal hydroxides With alkaline earth metal hydroxides, metal alkoxides, etc., in an inert atmosphere such as argon, nitrogen or helium It can be synthesized by performing the hydrogen halide reaction. The compounds having the structures represented by the following formulas (1), (3), (4) and (5) respectively correspond to the compounds indicated by the same reference numerals in FIG.

式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子であり、Ｒ_５１、Ｒ_６１、は、それぞれ独立にフッ素原子、臭素原子又は塩素原子である。ａ、ｂ、ｃ、ｄは０又は１の整数であり、ａ＋ｂ＋ｃ＋ｄ＝２〜４の何れかの整数である。

式中、Ｘ_１、Ｘ_２は、独立に臭素原子、塩素原子又はヨウ素原子であり、Ｒ_ａ、Ｒ_ｂは、独立に水素原子、アルキル基又はアリール基である。Ｙは、下記（Ｙ１）〜（Ｙ９）のいずれかで表される原子又は原子団であり、

式中、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆは、それぞれ独立に水素原子又は置換基である。

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom, and R ₅₁ and R ₆₁ each independently represent a fluorine atom, a bromine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and a + b + c + d is an integer in any one of 2 to 4.

In the formula, X ₁ and X _{2 each} independently represent a bromine atom, a chlorine atom or an iodine atom, and R _a and R _{b each} independently represent a hydrogen atom, an alkyl group or an aryl group. Y is an atom or atomic group represented by any of the following (Y1) to (Y9),

In the formula, Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent.

In the formula (1), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom And at least one of R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. In the present invention, heat resistance is imparted, chemical stability such as solvent resistance is improved, and fluorine-based solvent is introduced by introducing at least one fluorine atom having a large atomic radius into a hydrocarbon-based saturated cyclic structure. The above R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , and the like can be obtained because it is possible to obtain further effects on the improvement of the solubility in water and the addition of new functions (n-type semiconductor characteristics) caused by fluorine atoms. It is preferable that at least one of R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. Furthermore, if R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , and R ₄₂ are each a fluorine atom, the solubility in a fluorine-based solvent, the heat resistance and the solvent resistance are particularly remarkable. Improved, and a great effect can be obtained for imparting n-type semiconductor characteristics. Therefore, the fluorine-containing cyclic organic compound of the present invention more preferably has such a chemical structure.

  In the compound represented by the above formula (1), the number of carbon atoms constituting the hydrocarbon-based saturated cyclic structure is 2 to 4 as defined as any integer of a + b + c + d = 2 to 4 . When a + b + c + d = 2 to 4, not only the heat resistance, the solvent resistance and the solubility in a fluorine-based solvent can be improved, but also the raw materials can be easily obtained and the reaction during synthesis can be easily controlled. In order to sufficiently exert these effects, it is preferable that a + b + c + d = 3.

The compound represented by the formula (1) contains at least one of R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₅₁ and R ₆₁ substituted with a fluorine atom. It is a fluorine cycloalkene compound, and if it contains at least one fluorine atom, a compound containing a hydrogen atom, a bromine atom or a chlorine atom can be used. Among them, a compound containing a fluorine atom or a fluorine atom and a chlorine atom is preferable because the raw material can be easily obtained.

  Examples of cycloalkene compounds used in the present invention include 1,2,3,3,4,4,5,5-octafluorocyclopentene, 1,2,3,3,4,4-hexafluorocyclobutene, 1,2,3,3,4,4,5,5,6,6-defluorocyclohexene, 1,2,3,3,5,5-hexachlorodifluorocyclopentene, 1,2,3 or 1,2,3,1 4-Trichloropentafluorocyclopentene, 1,2,3,4-tetrachlorotetrafluorocyclopentene, 1,2,3,3,4-pentachlorotrifluorocyclopentene and the like. Furthermore, using octafluorocyclopentene or tetrachlorotetrafluoropentene from the viewpoint of availability of the material as a commercial product, easy control of the reaction at the time of synthesis, material cost etc., ie, a + b + c + d = 3 Is preferred.

In the compound which has a structure represented by said Formula (3)-(5), said X < ₁ >, X < ₂ > is a bromine atom, a chlorine atom, or an iodine atom independently. Among them, preferred is a bromine atom because it can suppress side reactions and enhance the reaction efficiency.

  Examples of the compound represented by the above formula (3) include tetrahydroxy-p-bromobenzene, tetrahydroxy-p-chlorobenzene, tetrahydroxy-1-bromo-4-iodobenzene, tetrahydroxy-1-bromo-4chlorobenzene and the like. Among them, it is preferable to use tetrahydroxy-p-bromobenzene from the viewpoint of high reaction efficiency and availability of raw materials.

In the above formula (4), R _a and R _b are independently a hydrogen atom, an alkyl group or an aryl group. Among them, a hydrogen atom is preferred in that the reaction efficiency can be increased. Examples of the compound containing the structural unit represented by the above formula (4) include 2,3-dihydroxy-1,4-dibromobenzene, 2,3-dihydroxy-1,4-dichlorobenzene, and 2,3-dihydroxy Examples thereof include -1,4-diiodobenzene, and compounds in which at least one of the 5- or 6-positions is nucleus-substituted with an alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group. Among these, it is preferable to use 2,3-dihydroxy-1,4-dibromobenzene in view of high reaction efficiency and availability of raw materials.

  In said Formula (5), Y is an atom or atomic group represented by either of said Formula (Y1)-(Y9). Among those atoms or atomic groups, those having a thiophene ring, a furan ring or a pyrrole ring represented by the above formula (Y1), (Y2) or (Y3) have reaction efficiency and ease of availability of raw materials It is preferable from the point of view. These rings can also be expected to exhibit new electric properties that have not been achieved by reacting with the compound represented by the formula (1). Examples of the compound represented by the formula (5) include 3,4-hydroxy-thiophene, 3,4-hydroxy-furan, 3,4-hydroxypyrrole and the like.

In the synthesis of the fluorine-containing π-conjugated polymer precursor monomer, each compound having a structure represented by the formula (1) and the formula (3), (4) or (5) is easily obtainable as a raw material Commercially available high purity materials can be used, but in some cases, synthetic products obtained by newly synthesizing from another raw material may be used as the raw material instead of the commercially available product. For example, tetrahydroxy-p-bromobenzene which is one of the compounds represented by the formula (3) can be synthesized by the method represented by the following reaction formula (16).

  As the solvent used when synthesizing the fluorine-containing π-conjugated polymer precursor monomer of the present invention, it is preferable to use a polar aprotic organic solvent such as DMSO as described above, but in addition to that, Nonpolar aprotic organic solvents such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, tripropylene Glycol ethers such as ethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated stone Naphtha, and the like may be used petroleum solvents such as solvent naphtha.

  Further, as described above, the catalyst used in the synthesis is a basic catalyst such as an alkali metal carbonate, an alkali metal phosphate, an alkali metal hydroxide, an alkali earth metal hydroxide, a metal alkoxide, etc. Is used. Examples of alkali metal carbonates include sodium carbonate, lithium carbonate, cesium carbonate, potassium carbonate and the like. Examples of alkali metal phosphates include sodium phosphate, potassium phosphate, cesium phosphate, lithium phosphate and the like. Examples of alkali metal hydroxides include sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide and the like. Examples of alkaline earth metal hydroxides include barium hydroxide and the like. Examples of metal alkoxides include sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and the like. Among them, potassium carbonate, sodium hydroxide, potassium hydroxide and potassium phosphate are preferably used in the present invention in terms of reaction efficiency, and potassium carbonate is more preferable.

  As shown in FIG. 2, the fluorine-containing π-conjugated cyclic polymer precursor monomer of the present invention has the following formula (2), instead of the compound having the structure represented by (1) as the compound (A): It can synthesize | combine using the compound represented by these.

式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は、Ｒ_１及び該Ｒ_１とシス位の置換基であるＲ_３がフッ素原子、臭素原子又は塩素原子であり、Ｒ_２、Ｒ_４がフッ素原子又はフッ素原子を１個以上含むアルキル基である。

In the formula, R ₁ , R ₂ , R ₃ and R _{4 each} represent R ₁ and R ₃ which is a substituent in the cis position with R ₁ are a fluorine atom, bromine atom or chlorine atom, and R ₂ and R ₄ are A fluorine atom or an alkyl group containing one or more fluorine atoms.

  As shown in FIG. 2, the fluorine-containing π-conjugated cyclic polymer precursor monomer [compounds represented by (23 M), (24 M), (25 M) in the figure] used in the present invention is represented by the above formula (2) It synthesizes by making the compound which has a structure represented, and the compound which has a structure represented by said Formula (3), (4), or (5) react. The synthesis method shown in FIG. 2 is basically the same as that shown in FIG. 1, and depending on the reaction conditions, the synthesis can be performed by appropriately selecting from the organic solvents and the catalyst described above.

In order for the fluorine-containing π-conjugated cyclic polymer precursor monomer [(23 M), (24 M), (25 M)] shown in FIG. 2 to have a hydrocarbon-based saturated cyclic structure, R shown in the above formula (2) _In R ₁ , R ₂ , R ₃ and R ₄ , R ₁ and R ₃ which is a substituent in the cis position with R ₁ must be a fluorine atom, a bromine atom or a chlorine atom. Furthermore, by introducing at least one fluorine atom having a large atomic radius into the hydrocarbon-based saturated cyclic structure, it is possible to impart heat resistance, improve chemical stability such as solvent resistance, and dissolve in a fluorine-based solvent. A further effect can be obtained with respect to the improvement of the property and the addition of new functions (such as n-type semiconductor characteristics) caused by the fluorine atom. Therefore, a fluorine-containing alkene compound in which the substituents R ₂ and R ₄ in the formula (2) are a fluorine atom or an alkyl group containing one or more fluorine atoms is used. Furthermore, if each of the hydrogen atoms contained in R ₂ and R ₄ is a fluorine atom, the solubility in a fluorine-based solvent, the heat resistance and the solvent resistance are remarkably improved, and the provision of the n-type semiconductor characteristics A great effect can be obtained. Therefore, the compound represented by the structure shown in the above (2) more preferably has a chemical structure in which the substituents R ₂ and R ₄ are a fluorine atom or a perfluoroalkyl group.

  As the fluorine-containing alkene compound used in the present invention, for example, tetrafluoroethene, 1,2-difluoro-1,2-dichloroethene, chlorotrifluoroethene, trifluoroethene, trichlorofluoroethene, hexafluoropropene, octafluoro Examples include -1-butene, octafluoro-2-butene, 1,2-dichlorohexafluoro-2-butene and the like. Furthermore, tetrafluoroethene, 1,2-difluoro-1,2-dichloroethene, chloro from the viewpoint of availability of the material as a commercial product, easy control of the reaction at the time of synthesis, material cost, and electrical characteristics etc. It is preferable to use an alkene compound containing a large amount of fluorine atoms, such as trifluoroethene, hexafluoropropene, octafluoro-1-butene and octafluoro-2-butene.

<Method for producing fluorine-containing π-conjugated cyclic polymer (homopolymer)>
Next, the method for producing the fluorine-containing π-conjugated cyclic polymer shown in FIGS. 1 and 2 will be described. Each compound having a chemical structure represented by the formulas (13M), (14M) and (15M) in FIG. 1 is polymerized by a homocoupling reaction using a transition metal compound as a catalyst, to obtain formulas (6) and (6) 7) A homopolymer of homopolymer having a single structural unit represented by (8) and (8) is produced. Similarly, compounds having chemical structures represented by the formulas (23M), (24M) and (25M) in FIG. 2 are also polymerized by homocoupling reaction using a transition metal compound as a catalyst to obtain formulas (9) respectively. , (10) and (11) to produce a homopolymer (homopolymer) of a homopolymer having a single structural unit.

  As the homocoupling reaction, known Ullmann reaction, Grasser reaction and the like are known. A transition metal such as nickel or copper or a transition metal complex thereof is used as a catalyst used for the homocoupling reaction, for example, bistriphenylphosphine nickel dichloride, 1,3-bis (diphenylphosphino) propane nickel dichloride And copper metals. In addition, a method for controlling and synthesizing a known π-conjugated polymer described in Non-Patent Document 1 may be employed.

Using a fluorine-containing π-conjugated cyclic polymer precursor monomer [(13 M) shown in FIG. 1] synthesized from the compound represented by the formula (1) and the compound represented by the formula (3) Examples of the fluorine-containing π-conjugated cyclic polymer produced and having a structural unit represented by the following formula (6) are listed below, but the present invention is not limited thereto.

Using a fluorine-containing π-conjugated cyclic polymer precursor monomer [(14 M) shown in FIG. 1] synthesized from the compound represented by the formula (1) and the compound represented by the formula (4) Examples of the fluorine-containing π-conjugated cyclic polymer produced and having a structural unit represented by the following formula (7) are listed below, but the present invention is not limited thereto.

A fluorine-containing π-conjugated cyclic polymer precursor monomer [(15 M) shown in FIG. 1] synthesized from the compound represented by the formula (1) and the compound represented by the formula (5) Examples of the fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (8) are listed below, but the present invention is not limited thereto.

Using a fluorine-containing π-conjugated cyclic polymer precursor monomer [(23 M) shown in FIG. 2] synthesized from the compound represented by the formula (2) and the compound represented by the formula (3) Examples of the fluorine-containing π-conjugated cyclic polymer produced and having a structural unit represented by the following formula (9) are listed below, but the present invention is not limited thereto.

Using a fluorine-containing π-conjugated cyclic polymer precursor monomer [(24 M) shown in FIG. 2] synthesized from the compound represented by the formula (2) and the compound represented by the formula (4) Examples of the fluorine-containing π-conjugated cyclic polymer produced and having a structural unit represented by the following formula (10) are shown below, but the present invention is not limited thereto.

Using a fluorine-containing π-conjugated cyclic polymer precursor monomer [(25 M) shown in FIG. 2] synthesized from the compound represented by the formula (2) and the compound represented by the formula (5) Examples of the fluorine-containing π-conjugated cyclic polymer produced and having a structural unit represented by the following formula (11) are listed below, but the present invention is not limited thereto.

<Method for producing fluorine-containing π-conjugated cyclic polymer (copolymer)>
The fluorine-containing π-conjugated cyclic polymer of the present invention can be produced as a copolymer in addition to the homopolymer. In that case, each compound having a chemical structure represented by the formulas (13M), (14M) and (15M) shown in FIG. 1 or a formula (23M), (24M) and (25M) shown in FIG. Each compound having the chemical structure to be copolymerized is copolymerized by performing a cross coupling reaction with another π-conjugated polymer precursor monomer. Thereby, in addition to any of the structural units represented by the above formulas (6), (7), (8), (9), (10) and (11), 13) A copolymer having at least one of the structural units represented by (14) and (15) can be produced.

式中、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０は、それぞれ独立に水素原子、アルキル基又はアルコキシ基を示し、ｅ、ｇ、ｈは１〜４のいずれかの整数で、ｆは１〜２のいずれかの整数である。Ｚは、下記（Ｚ１）〜（Ｚ９）のいずれかで表される原子又は原子団である。

式中、Ｒｇ、Ｒｈ、Ｒｉ、Ｒｊは、それぞれ独立に水素原子又は置換基である。

In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and e, g, h are integers of 1 to 4 and f is 1 to Any integer of 2. Z is an atom or atomic group represented by any of the following (Z1) to (Z9).

In the formula, Rg, Rh, Ri and Rj are each independently a hydrogen atom or a substituent.

  In said Formula (13), Z is an atom or atomic group represented by either of said Formula (Z1)-(Z9). Among these atoms or atomic groups, a structure having a thiophene ring, a furan ring or a pyrrole ring represented by the above formula (Z1), (Z2) or (Z3) is a point of reaction efficiency and ease of availability of raw materials It is preferable from These rings can also be expected to exhibit new electric properties that have not been achieved by copolymerizing them with fluorine-containing π-conjugated cyclic polymer precursor monomers. The structural unit represented by the above formula (13) is, for example, thiophene in which the 3-position or 3- or 4-position is substituted with an alkyl group, thiophene ring in which the 3-position or 3- or 4-position is substituted with an alkoxy group, 3-position or A furan ring in which the 3,4-position is substituted with an alkyl group, a furan ring in which the 3-position or the 3,4-position is substituted with an alkoxy group, a pyrrole ring in which the 3-position or the 3,4-position is substituted with an alkyl group, the 3-position Or a pyrrole ring in which the 3,4-position is substituted with an alkoxy group.

  As a cross coupling reaction utilized when manufacturing a copolymer as said fluorine-containing pi conjugated cyclic polymer, transition metal complexes, such as palladium, are used as a catalyst, For example, a halide and an aryl boronic acid derivative or boron The Suzuki reaction known as the reaction with an acid ester, or the Heck reaction, the Sonogashira reaction, the Negishi reaction, etc. can be used besides this. In addition, a method for controlling and synthesizing a known π-conjugated polymer described in Non-Patent Document 1 may be employed.

  In the fluorine-containing π-conjugated cyclic polymer of the present invention, in the case of producing a copolymer by using the cross coupling reaction, the above formulas (6), (7), (8), (9), ( 10) An alternate embodiment in which any of the structural units represented by (11) and (11) and any of the structural units represented by the above formulas (12), (13), (14) and (15) are alternately chemically bonded It is preferable to use a polymer. The alternating copolymer not only can increase the yield of the synthetic object due to the improvement of reaction efficiency, but also can obtain high stereoregularity in the fluorine-containing π-conjugated cyclic polymer, and the intermolecular and intermolecular high π conjugation It is possible to form a system.

  Any of the structural units represented by the formulas (6), (7), (8), (9), (10) and (11), and the formulas (12), (13), (14) and ( An example of the manufacturing method of the alternating copolymer which chemically bonded alternately with any of the structural units represented by 15), and the example of the copolymer obtained by this manufacturing method are each shown in FIGS. 3 to 13 show fluorine-containing π-conjugated cyclic polymer precursor monomers and copolymers as “fluorine-containing polyphenylene precursors (monomers)” and “fluorine-containing polyphenylenes” (FIG. 3, FIGS. 6 to 6). 7 and FIGS. 9 to 11), or “fluorinated copolymer precursor (monomer)” and “fluorinated copolymer” (FIGS. 4 to 5, 8 and 12 to 13) The invention is not limited to these examples.

In FIG. 3, the example of the manufacturing method of the alternating copolymer which has a structural unit represented by said Formula (6) and said Formula (12), and the example of the alternating copolymer manufactured by this manufacturing method are shown. In FIG. 3, in the structural units represented by the above formula (6), when R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, a + b + c + d = 3 is there. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

In FIG. 4, the example of the manufacturing method of the alternating copolymer which has a structural unit represented by said Formula (6) and said Formula (13), and the example of the alternating copolymer manufactured by this manufacturing method are shown. In FIG. 4, in the structural units represented by the above formula (6), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, and a + b + c + d = 3 is there. In the structural unit represented by the above formula (13), Z is a thiophene ring of Z1, and the 3-position of the thiophene ring is an alkyl group of -C _n H _{2n + 1} (n = 6, 8, 10 or 12) Is replaced by

In FIG. 5, the example of the manufacturing method of the alternating copolymer which has a structural unit represented by said Formula (6) and said Formula (14), and the example of the alternating copolymer manufactured by this manufacturing method are shown. In FIG. 5, in the structural units represented by the formula (6), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, and a + b + c + d = 3 is there. In the structural unit represented by the above formula (14), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 6 shows another example of the method for producing the alternating copolymer having the structural units represented by the above-mentioned formula (6) and the above-mentioned formula (12) and another example of the alternating copolymer produced by this production method. An example is shown. In FIG. 6, in the structural unit represented by the above formula (6), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, and a + b + c + d = 2 is there. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 7 shows another example of the method for producing the alternating copolymer having the structural units represented by the above formula (6) and the above formula (12), and another example of the alternating copolymer produced by the method. An example is shown. In FIG. 7, in the structural units represented by the above formula (6), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, and a + b + c + d = 4 is there. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 8 shows another example of the method for producing the alternating copolymer having the structural units represented by the above formula (6) and the above formula (14), and another example of the alternating copolymer produced by the method. An example is shown. In FIG. 8, two of the structural units represented by the formula (6) are R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ , and the remaining is a fluorine atom, Is a chlorine atom, and a + b + c + d = 3. In the structural unit represented by the above formula (14), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 9 shows an example of a method of producing an alternating copolymer having the structural units represented by the formula (7) and the formula (12), and an example of an alternating copolymer produced by the method. In FIG. 9, in the structural units represented by the above formula (7), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ are fluorine atoms, and a + b + c + d = 3 is there. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 10 shows an example of a method of producing an alternating copolymer having the structural units represented by the above formula (9) and the above formula (12), and an example of an alternating copolymer produced by the method. In FIG. 10, in the structural unit represented by the formula (9), R ₂ is a perfluoromethyl group, and R ₄ is a fluorine atom. In addition, the structural unit represented by the formula (12) has an alkyl group (n = 6, 8, 10 or 12) in which the 2,5 position is -C _n H _{2n + 1} , or an -OC _n H in the 2,5 position. It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 11 shows an example of a method of producing an alternating copolymer having a structural unit represented by the above formula (10) and the above formula (12) and an example of an alternating copolymer produced by the method. In FIG. 11, in the structural unit represented by the formula (10), R ₂ is a perfluoromethyl group, and R ₄ is a fluorine atom. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 12 shows an example of a method of producing an alternating copolymer having the structural units represented by the formula (8) and the formula (12), and an example of an alternating copolymer produced by the method. In FIG. 12, the structural unit represented by the above formula (8) is a thiophene ring in which Y is Y1, and R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ are It is a fluorine atom, and a + b + c + d = 3. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

FIG. 13 shows an example of a method of producing an alternating copolymer having the structural units represented by the formula (11) and the formula (12), and an example of an alternating copolymer produced by the production method. In FIG. 13, in the structural unit represented by the formula (11), Y is a thiophene ring, R ₂ is a perfluoromethyl group, and R ₄ is a fluorine atom. In the structural unit represented by the above formula (12), the 2,5 position is an alkyl group (n = 6, 8, 10 or 12) of -C _n H _{2n + 1} , or the 2,5 position is -OC _n H It has a benzene ring nuclear-substituted by _{2n + 1} alkoxy groups (n = 6, 8, 10 or 12).

  The copolymer produced as described above can form a π-conjugated system continuously in the main chain of the molecule as the fluorine-containing π-conjugated cyclic polymer of the present invention, similarly to the homopolymer. Furthermore, the solubility in a common organic solvent is high, the film forming property is good, and since it has a saturated cyclic structure, it is also excellent in stability and durability. Therefore, when the fluorine-containing π-conjugated cyclic polymer of the present invention is applied as an electronic material, polymers having various structures can be produced according to the physical properties and characteristics required at the time of actual application. , A significant expansion of the scope of application is expected.

(Organic light emitting element)
Next, an organic light emitting device will be described as one application example of the fluorine-containing π-conjugated cyclic polymer of the present invention. The organic light emitting element to be produced is an element in which a single layer or a multilayer organic thin film is laminated between an anode and a cathode. When the organic light emitting element is a single layer, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and further contains a hole transporting material or an electron transporting material for the purpose of transporting holes injected from the anode or holes injected from the cathode to the light emitting material. The light-emitting element used herein has a single material having hole transporting ability and / or electron transporting ability in addition to light emitting ability, or a mixture of compounds having the respective characteristics. Useful for The fluorine-containing π-conjugated cyclic polymer of the present invention is used as a light emitting material.

Examples of the multilayer organic light emitting device include a structure in which the following multilayer structure is laminated on a substrate.
(1-1) Anode / hole transport layer / light emitting layer / cathode (1-2) anode / light emitting layer / electron transport layer / cathode (1-3) anode / hole transport layer / light emitting layer / electron transport layer / Cathode (1-4) anode / hole injection layer / hole transport layer / emission layer / electron transport layer / cathode (1-5) anode / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode (1-6) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  In addition to the above configuration, if necessary, a layer in which a hole transport layer component and a light emitting layer component, or an electron transport layer component and a light emitting layer component are mixed may be provided. Furthermore, between the electron transport layer and the light emitting layer, a layer (hole blocking layer) that inhibits holes or excitons (exxtons) from coming off to the cathode side, or a light emitting layer in an excited state, or light emission in an excited state A layer (anti-quenching layer) may be inserted to prevent or suppress both energy transfer and electron transfer from one layer to an adjacent layer.

  In the configuration of these multilayer organic light emitting devices, the fluorine-containing π-conjugated cyclic polymer of the present invention is used as the light emitting material contained in the light emitting layer.

  The organic light emitting device of the present invention can be provided with a protective layer (sealing layer) for blocking the contact with oxygen, moisture and the like so as not to be affected by the external environment as much as possible, in addition to the above configuration. . The protective layer can be formed using any of an epoxy resin, an acrylic resin, a polyester resin, a polycarbonate resin, a thermoplastic resin such as a fluorine resin, a thermosetting resin, and a photocurable resin. In addition, the organic light emitting device of the present invention can be protected from the external environment by enclosing the device in an inert substance such as paraffin, silicone oil, fluorocarbon or the like.

  Hereinafter, the configuration of the organic light emitting device of the present invention will be described in detail by taking, as an example, the configuration in which the above (1-3) anode, hole transport layer, light emitting layer, electron transport layer and cathode are sequentially provided on a substrate. Do.

  The substrate is not particularly limited as long as it is used in a conventional organic light emitting device, and examples thereof include a substrate made of a material such as glass such as quartz glass and transparent plastic. Alternatively, an opaque substrate such as a metal substrate or a ceramic substrate may be used.

  As the anode, one having a large work function is preferable. For example, metals such as gold, platinum, nickel, palladium, cobalt, selenium, vanadium or the like, or alloys thereof, oxides, zinc oxide, indium tin oxide (ITO And metal oxides such as zinc indium oxide. Also, conductive polymer materials such as polyaniline, polypyrrole and polythiophene can be used. The anode can form these materials on a substrate by, for example, a method such as vapor deposition, sputtering, or application. The film thickness of the anode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  As a hole transport material used for the said hole transport layer, the thing currently used as a charge injection transport material of the hole in a photoconductive material from the former, and the well-known used for the hole transport layer of an organic light emitting element It can be selected arbitrarily from the materials. Examples of the hole transport material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ', N'-tetraphenyl-1,4-phenylenediamine, N, N'-di (m-tolyl) -N Triaryls such as N, N'-diphenyl-4,4'-diaminobiphenyl (TPD), N, N'-di (1-naphthyl) -N, N'-diphenyl-4,4'-diaminobiphenyl (α-NPD) Amine derivatives, polyphenylene vinylene derivatives, polythiophene derivatives and the like can be mentioned. In addition, hole transporting polymers such as polyvinyl carbazole, (phenylmethyl) polysilane, polyaniline and the like can also be used. As the hole transporting polymer, one obtained by doping the low molecular weight hole transporting material with a polymer such as polystyrene or polycarbonate may be used.

  As the light emitting material used for the light emitting layer, the fluorine-containing π-conjugated cyclic polymer of the present invention is used, but in addition to this, it may be used in combination with a conventionally known compound as a light emitting material. As known light emitting materials, acridone derivatives, quinacridone derivatives, coumarin derivatives, pyran derivatives, oxazone derivatives, benzooxazone derivatives, benzothiazole derivatives, benzimidazole derivatives, fused polycyclic aromatic hydrocarbons and derivatives thereof, triarylamine derivatives, Organometallic derivatives (for example, organometal complexes of aluminum or iridium) and the like can be mentioned, and they can be used alone or in combination of two or more. In addition, as the light emitting material, a material in which a host material contains a dopant material, for example, a polycarbazole doped with an iridium metal complex or a charge transporting host material containing a phosphorescent platinum complex can be used.

Examples of the electron transport material used for the electron transport layer include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq ₃ ), 2- (4-biphenylyl) -5- (4-) t-Butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole Examples include azole compounds such as (TAZ) and phenanthroline derivatives.

  As the cathode, one having a small work function is preferable. For example, a single metal or a plurality of alloys such as lithium, sodium, potassium, cesium, calcium, magnesium, aluminum, indium, silver, lead, tin, chromium and the like can be mentioned. Be In addition, metal oxides such as indium tin oxide (ITO) may be used. The cathode can be produced by forming a thin film of these materials by, for example, a method such as vapor deposition or sputtering. The thickness of the cathode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  In the above organic light emitting device, the light emitting layer containing the fluorine-containing π-conjugated cyclic polymer of the present invention is generally dissolved in a vacuum evaporation method or an applicable organic solvent to form a solution, and the solution is spin-coated and diped A thin film is formed by a coating method such as coating or roll-to-hole method. The copolymer of the present invention can obtain good film formability in film formation by a solution coating method. Therefore, especially when manufacturing a device with high definition and large area, improvement of workability and reduction of manufacturing cost can be achieved. Can produce great effects. Examples of the organic solvent to be used include hydrocarbon solvents, ketone solvents, halogen solvents, ester solvents, alcohol solvents, ether solvents, aprotic solvents, perfluoro solvents, water and the like. These organic solvents may be used alone or as a mixture of solvents.

  The film thickness of each layer such as the above-mentioned hole transport layer, light emitting layer, electron transport layer, etc. is not particularly limited as long as it is a film thickness generally adopted in conventional organic light emitting devices, but usually 1 to 1000 nm. To be adjusted.

  The fluorine-containing π-conjugated cyclic polymer of the present invention can be mainly used as a light emitting material, but may also be used as an electron transporting material or a charge transporting material according to the electronic state of the repeating unit.

  The fluorine-containing π-conjugated cyclic polymer of the present invention can be used not only as the organic light-emitting device described above, but also as a material of an active layer (n layer) or charge transport layer constituting an electrode of a solar cell. .

  Hereinafter, although it demonstrates using a specific Example, this invention is not limited at all by these Examples.

Example 1
[Synthesis of Fluorine-Containing π-Conjugated Cyclic Polymer Precursor Monomer]
The synthesis method of the precursor monomer 1 used when manufacturing the fluorine-containing pi-conjugated cyclic polymer of the illustration number 6-1 is shown next.

  The precursor monomer 1 used as the raw material of the fluorine-containing pi conjugated cyclic polymer of the illustration number 6-1 was specifically synthesize | combined according to the following procedures based on said chemical reaction formula. 3.5 g of dihydroxybenzoquinone (a) was suspended in chloroform and cooled to 0 ° C. After that, bromine (2.8 ml) was added and stirred overnight. The suspension was filtered and the residue was dissolved in aqueous sodium hydroxide solution and then a precipitate formed on addition of concentrated hydrochloric acid. The precipitate was isolated by filtration and dried to give 7.01 g of bromanic acid (b).

Then, 1.48 g (5 mmol) of bromanic acid (b) was dissolved in 40 ml of ethyl acetate under an argon atmosphere, 20 ml of an aqueous solution of sodium hydrosulfite (Na ₂ S ₂ O ₄ ) was added, and the mixture was stirred overnight. The reaction solution was extracted with ethyl acetate, and the organic solvent was evaporated under reduced pressure to obtain 1.46 g (4.86 mmol) of tetrahydroxy-p-bromobenzene (c).

1.46 g of tetrahydroxy-p-bromobenzene (c) thus obtained was dissolved in DMSO (10 ml) under an argon atmosphere, 4.83 g (35 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature for 10 minutes. After that, 2.2 g (10 mmol) of octafluorocyclopentene (d) was added and stirred overnight at room temperature. After adding 50 ml of water, 3 N hydrochloric acid was dropped little by little to cause precipitation. The precipitate was separated by filtration and dried to obtain 1.85 g (yield 64%) of a fluorine-containing π-conjugated polymer precursor monomer 1 as a white solid. The structure of the fluorine-containing π-conjugated polymer precursor monomer 1 was specified by ¹⁹ F NMR and X-ray crystal structure analysis.

The measurement of the NMR spectrum is carried out by adding a sample and a deuterated chloroform solvent (CDCl ₃ ) into a sample tube of 5φ, using tetramethylsilane (TMS) as an internal standard, and using an NMR apparatus (Bruker AVANCE III type 400) The The peak shown next was observed by 19 F-NMR measurement.
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ -127.5 (m, 2F), -117.1 (m, 1F).

In addition, X-ray structural analysis is performed using a Rigaku desktop single crystal X-ray structural analyzer XtaLABmini using 50kV, 12mA, 0.60kW power, 600W X-ray output, and a MARCURY CCD as a detector, a spectroscope As condensing element SHINE, as analysis software olex 2 and marcury were used respectively. The crystal structure estimated by X-ray structural analysis is shown in FIG.

  As a result of X-ray structural analysis, as shown in FIG. 14, the fluorine-containing π-conjugated polymer precursor monomer 1 has a cyclic crystal structure close to a plane, and the plane portion shows the expression of π-conjugation. It is easily guessed that they will make a major contribution.

[Production of Fluorine-Containing π-Conjugated Cyclic Polymer (Homopolymer) of Example No. 6-1]
Using the fluorine-containing π-conjugated polymer precursor monomer 1, a homopolymer (example number 6-1) of a fluorine-containing π-conjugated cyclic polymer was produced according to the method shown below.

3.18 g (5.5 mmol) of fluorine-containing π-conjugated polymer precursor monomer 1 was dissolved in THF (10 ml) under an argon atmosphere, an isopropyl magnesium chloride lithium chloride reagent was added, and the mixture was stirred at 0 ° C. for 1 hour. Next, catalyst bistriphenylphosphine nickel dichloride (10 mol%) was added and stirred overnight at room temperature. Thereafter, the reaction solution was dropped into 150 ml of methanol, and then hydrochloric acid was dropped little by little to precipitate a solid. The precipitate was separated by filtration and dried to obtain 1.8 g (yield 78%) of a homopolymer. As a result of specifying the structure by ¹⁹ F NMR, it was confirmed that the homopolymer thus produced had a structural unit shown by the example No. 6-1 as shown below.
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ -127.9 (m, 2F), -117.3 (m, 1F).

Example 2
[Synthesis of Fluorine-Containing π-Conjugated Cyclic Polymer (Copolymer) of Example No. 12-1]
Using the fluorine-containing π-conjugated polymer precursor monomer 1 synthesized in Example 1 according to the method described below for the fluorine-containing π-conjugated cyclic polymer (copolymer) of the example number 12-1 shown in FIG. 3 Manufactured.

A solution of 2.5 g (5 mmol) of fluorine-containing π-conjugated cyclic polymer precursor monomer 1 and 1.2 g (5 mmol) of benzenediboronic acid pinacol ester (e) in THF was dissolved in X-Phos (2-dicyclohexylphos After adding 0.19 g of fino-2 ', 4', 6'-triisopropylbiphenyl, 0.55 g of palladium acetate and 10 ml of saturated aqueous potassium carbonate solution, the mixture was stirred at 50 ° C for 24 hours. The reaction solution was cooled to room temperature and then dropwise added to 150 ml of methanol, and then hydrochloric acid was dropped little by little to precipitate a solid. The precipitate was separated by filtration, the residue was dissolved in dichloromethane and reprecipitated dropwise into hexane. The precipitate was again filtered and dried to obtain 0.33 g (yield 11%) of a copolymer. As a result of specifying the structure by ¹ H NMR and ¹⁹ F NMR, the copolymer (copolymer) thus produced has a structural unit shown by the example No. 12-1 in FIG. 3 as shown next. confirmed.
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.73 (brs, 2H), 7.39 (brs, 2H).
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ -127.5 (m, 2F), -117.2 (m, 1F).

  As described above, according to the method for producing a fluorine-containing π-conjugated cyclic polymer of the present invention, a homopolymer and a copolymer of a fluorine-containing π-conjugated cyclic polymer are obtained using easily available raw materials. It can be obtained with a smaller number of synthetic steps than before. In addition, the fluorine-containing π-conjugated cyclic polymer obtained by the production method of the present invention has high solubility in an organic solvent and good film-forming properties, while sufficiently exhibiting π electron conjugation. Excellent in durability. Furthermore, since it is possible to produce fluorine-containing π-conjugated cyclic polymers having various structures according to the physical properties and characteristics required as electronic materials, electronic devices and solar cells having high performance and new functions, etc. Its usefulness is extremely high because it can be expected to be applied to a wide range of fields.

Claims (14)

Process for producing fluorine-containing π-conjugated cyclic polymer produced by homopolymerization or copolymerization of fluorine-containing π-conjugated cyclic polymer precursor monomer by homo-coupling reaction or cross-coupling reaction using transition metal catalyst And
The fluorine-containing π-conjugated cyclic polymer precursor monomer is
A monocyclic or chain compound (A) having one double bond and one or more fluorine atoms in one molecule,
a compound (B) which is a π-conjugated cyclic compound and which has, as a nuclear substituent, 2 or 4 hydroxyl groups in the ortho position and a bromine atom, chlorine atom or iodine atom in the para position;
A process for producing a fluorine-containing π-conjugated cyclic polymer, which is synthesized by the reaction of The compound (A) is a compound having a structure represented by the following formula (1) or (2),
The production of the fluorine-containing π-conjugated cyclic polymer according to claim 1, wherein the compound (B) is a compound having a structure represented by the following formula (3), (4) or (5): Method.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom, and R ₅₁ and R ₆₁ each independently represent a fluorine atom, a bromine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and a + b + c + d is an integer in any one of 2 to 4. In R ₁ , R ₂ , R ₃ and R ₄ , R ₁ and R ₃ which is a substituent in the cis position with R ₁ are a fluorine atom, a bromine atom or a chlorine atom, and R ₂ and R ₄ are a fluorine atom Or an alkyl group containing one or more fluorine atoms.

In the formula, X ₁ and X _{2 each} independently represent a bromine atom, a chlorine atom or an iodine atom, and R _a and R _{b each} independently represent a hydrogen atom, an alkyl group or an aryl group. Y is an atom or atomic group represented by any of the following (Y1) to (Y9),

In the formula, Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent. R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₅₁ , R ₆₁ , R ₁ and R ₃ are each a fluorine atom, and R ₂ and R 3 _The method for producing a fluorine-containing π-conjugated cyclic polymer according to claim 2, wherein ₄ is independently a fluorine atom or a perfluoroalkyl group.   The method for producing a fluorine-containing π-conjugated cyclic polymer according to claim 2 or 3, wherein the a + b + c + d is an integer of a + b + c + d = 3. The method for producing a fluorine-containing π-conjugated cyclic polymer according to any one of claims 2 to 4, wherein X ₁ and X ₂ are a bromine atom. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing (pi) conjugated system cyclic compound synthesize | combined from the compound represented by the said Formula (1), and the compound represented by the said Formula (3) A method for producing a fluorine-containing π-conjugated cyclic polymer, which comprises producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (6) using a polymer precursor monomer.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing (pi) conjugated system cyclic compound synthesize | combined from the compound represented by the said Formula (1), and the compound represented by the said Formula (4) A process for producing a fluorine-containing π-conjugated cyclic polymer, which comprises producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (7) using a polymer precursor monomer.

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. R _a and R _b are independently a hydrogen atom, an alkyl group or an aryl group. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing pi-conjugated system synthesize | combined from the compound represented by the said Formula (1), and the compound represented by the said Formula (5) A process for producing a fluorine-containing π-conjugated cyclic polymer, which comprises producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (8) using a cyclic polymer precursor monomer: .

In the formulae, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and R ₁₁ and R ₁₂ And at least one of R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom. Y is the same atom or atomic group as the atom or atomic group represented by any one of (Y1) to (Y9) above. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing (pi) conjugated system cyclic compound synthesize | combined from the compound represented by the said Formula (2), and the compound represented by the said Formula (3) A method for producing a fluorine-containing π-conjugated cyclic polymer, which comprises producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (9) using a polymer precursor monomer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing (pi) conjugated system cyclic compound synthesize | combined from the compound represented by the said Formula (2), and the compound represented by the said Formula (4) A process for producing a fluorine-containing π-conjugated cyclic polymer, which comprises producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (10) using a polymer precursor monomer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms, and R _a and R _{b each} independently represent a hydrogen atom, an alkyl group or an aryl group. In the manufacturing method as described in any one of Claims 2-5, the fluorine-containing (pi) conjugated system cyclic compound synthesize | combined from the compound represented by the said Formula (2), and the compound represented by the said Formula (5) A method for producing a fluorine-containing π-conjugated cyclic polymer, comprising producing a fluorine-containing π-conjugated cyclic polymer having a structural unit represented by the following formula (11) using a polymer precursor monomer.

In the formula, R ₂ and R _{4 each} represent a fluorine atom or an alkyl group containing one or more fluorine atoms. Y is the same atom or atomic group as the atom or atomic group represented by any one of (Y1) to (Y9) above. Further, by cross-coupling reaction of the fluorine-containing π-conjugated cyclic polymer precursor monomer with a π-conjugated polymer precursor monomer different from the fluorine-containing π-conjugated cyclic polymer precursor monomer, The copolymer having at least one of the structural units represented by the formulas (12), (13), (14) and (15) is produced. The manufacturing method of the fluorine-containing pi conjugated cyclic polymer as described.

In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and e, g, h are integers of 1 to 4 and f is 1 to Any integer of 2. Z is an atom or atomic group represented by any of the following (Z1) to (Z9),

In the formula, Rg, Rh, Ri and Rj are each independently a hydrogen atom or a substituent.   The copolymer is a structural unit formed in the fluorine π-conjugated cyclic polymer by polymerization of the fluorine-containing π-conjugated cyclic polymer precursor monomer, and the formulas (12), (13), and (14) 13. The method for producing a fluorine-containing &pgr; -conjugated cyclic polymer according to claim 12, which is an alternating copolymer in which any of the structural units represented by) and (15) are chemically bonded alternately.   A light emitting device comprising the fluorine-containing π-conjugated cyclic polymer produced by the method according to any one of claims 1 to 13 as a light emitting material of a light emitting layer.

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