JP2013227307A - New compound and polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound which is designed for the purpose of usefully exploiting a structure of a dibenzo[g, p]chrysene skeleton.SOLUTION: A compound is represented by formula (C1) wherein each of Rto Ris a univalent functional group respectively and independently including a univalent functional group including H, X, and N or O, however, cases where any of following (1) to (4) holds are excluded. (1) All of Rto Rare hydrogen atoms. (2) Ris Br at position 2, Ris Br at position 10, and Rand Rare H. (3) A univalent functional group including N is -N(Ph). (4) Ris an -OH group at position 3, Ris an -OH group at position 11, and Rand Rare H.

Description

  The present invention relates to a novel compound and a polymer using the same, and more particularly to a novel compound having a dibenzo [g, p] chrysene skeleton and a polymer using the same.

  Conventionally, a compound group having a dibenzo [g, p] chrysene skeleton has attracted attention as a material exhibiting organic electroluminescence characteristics. And the various dibenzo [g, p] chrysene compound groups substituted by the bulky functional group which has an aromatic ring structure are indicated by the following patent documents 1-4.

JP 2002-237384 A JP 2009-292807 A JP 2004-182737 A WO09 / 107549 pamphlet

However, the synthesis of compounds utilized for other uses utilizing the structure of the dibenzo [g, p] chrysene skeleton has not progressed. Accordingly, the present inventors have attempted to synthesize novel compounds that take advantage of the characteristics of the dibenzo [g, p] chrysene skeleton.
The present invention has been made in view of the above-described situation, and is a novel design designed to make more effective use of the structure of the dibenzo [g, p] chrysene skeleton for purposes other than utilizing the function of organic electroluminescence. It is an object to provide a novel compound and a polymer using the same.

〔式（Ｃ１）中、Ｒ^１〜Ｒ^４は、各々独立に、Ｈ（水素原子）、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又は、Ｓ（硫黄原子）を含む１価の官能基である。但し、下記（１）〜（６）のいずれかである場合を除く。〕
（１）Ｒ^１〜Ｒ^４の全てがＨ（水素原子）である。
（２）Ｒ^１が２位においてＢｒであり、Ｒ^３が１０位においてＢｒであり、且つＲ^２及びＲ^４がＨである。
（３）上記Ｎを含む１価の官能基が−Ｎ（Ｐｈ）_２である。
（４）Ｒ^１が３位においてヒドロキシル基であり、Ｒ^３が１１位においてヒドロキシル基であり、且つＲ^２及びＲ^４がＨである。
（５）Ｒ^１が３位においてメトキシ基であり、Ｒ^３が１１位においてメトキシ基であり、且つＲ^２及びＲ^４がＨである。
（６）Ｒ^１が３位においてトシル基であり、Ｒ^３が１１位においてトシル基であり、且つＲ^２及びＲ^４がＨである。 In order to solve the above problems, the gist of the compound according to claim 1 is a compound represented by the following formula (C1).

[In Formula (C1), R ^{1 to} R ⁴ each independently include a monovalent functional group containing H (hydrogen atom), X (halogen atom), or N (nitrogen atom), or O (oxygen atom). It is a monovalent functional group or a monovalent functional group containing S (sulfur atom). However, the case of any of (1) to (6) below is excluded. ]
(1) All of R ^{1 to} R ⁴ are H (hydrogen atom).
(2) R ¹ is Br at the 2-position, R ³ is Br at the 10-position, and R ² and R ⁴ are H.
(3) The monovalent functional group containing N is —N (Ph) ₂ .
(4) R ¹ is a hydroxyl group at the 3-position, R ³ is a hydroxyl group at the 11-position, and R ² and R ⁴ are H.
(5) R ¹ is a methoxy group at the 3-position, R ³ is a methoxy group at the 11-position, and R ² and R ⁴ are H.
(6) R ¹ is a tosyl group at the 3-position, R ³ is a tosyl group at the 11-position, and R ² and R ⁴ are H.

The gist of the compound according to claim 2 is that, in claim 1, at least one of R ^{1 to} R ⁴ is a monovalent functional group containing N.

The gist of the compound according to claim 3 is that in claim 2, the monovalent functional group containing N is —NH ₂ .

〔但し、式（Ｃ２）中、Ｒ^５及びＲ^６は、各々独立に、炭素数１〜３の直鎖又は分枝のアルキレン基である。〕 The gist of the compound according to claim 4 is that, in claim 2, the monovalent functional group containing N is represented by the following formula (C2).

[In the formula (C2), R ⁵ and R ⁶ are each independently a linear or branched alkylene group having 1 to 3 carbon atoms. ]

The gist of the compound according to claim 5 is that, in claim 1, at least one of R ^{1 to} R ⁴ is a monovalent functional group containing O.

  The compound according to claim 6 is summarized in that, in claim 5, the monovalent functional group containing O is —OH.

〔但し、式（Ｃ３）中、Ｒ^７は炭素数１〜３の直鎖又は分枝のアルキレン基である〕 The gist of the compound according to claim 7 is that, in claim 5, the monovalent functional group containing O is represented by the following formula (C3).

[In the formula (C3), R ⁷ is a linear or branched alkylene group having 1 to 3 carbon atoms]

The gist of the compound according to claim 8 is that, in claim 1, at least one of R ^{1 to} R ⁴ is a monovalent functional group containing S.

  The gist of the compound according to claim 9 is that the monovalent functional group containing S is -SH.

  The gist of the polymer according to claim 10 is obtained by using any of the compounds according to claims 1 to 9.

  According to the present invention, the structure of the dibenzo [g, p] chrysene skeleton can be utilized more effectively for purposes other than utilizing the function of organic electroluminescence.

2 is a mass spectrum of the compound 31 according to Example 2. 2 is a mass spectrum of the compound 32 according to Example 2. 3 is a mass spectrum of the compound 33 according to Example 2. 3 is a mass spectrum of the compound 34 according to Example 2. 3 is a mass spectrum of the compound 41 according to Example 3. 4 is a mass spectrum of the compound 42 according to Example 3. 4 is a mass spectrum of the compound 43 according to Example 3. 4 is a mass spectrum of the compound 44 according to Example 3. 4 is a mass spectrum of the compound 51 according to Example 4. 4 is a mass spectrum of the compound 52 according to Example 4. 4 is a mass spectrum of the compound 53 according to Example 4. 7 is a mass spectrum of the compound 71 according to Example 6. 4 is a mass spectrum of the compound 72 according to Example 6. 6 is a mass spectrum of the compound 73 according to Example 6. 4 is a mass spectrum of the compound 74 according to Example 6. 4 is a mass spectrum of the compound 91 according to Example 8. 4 is a mass spectrum of the compound 92 according to Example 8. 10 is a multiplex chart showing thermal analysis results according to Example 9. 2 is a ¹ H-NMR chart of Compound 74 according to Example 11. 20 is a ¹ H-NMR chart of Compound 74 according to Example 11, which is an enlarged chart of a portion of FIG. 10 is a ¹³ C-NMR chart of Compound 74 according to Example 11. FIG. 22 is a ¹³ C-NMR chart of the compound 74 according to Example 11, and is a chart showing a part of FIG. 21 in an enlarged manner.

〔式（Ｃ１）中、Ｒ^１〜Ｒ^４は、各々独立に、Ｈ（水素原子）、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又は、Ｓ（硫黄原子）を含む１価の官能基である。但し、下記（１）〜（６）のいずれかである場合を除く。〕
（１）Ｒ^１〜Ｒ^４の全てがＨ（水素原子）である。
（２）Ｒ^１が２位においてＢｒであり、Ｒ^３が１０位においてＢｒであり、且つＲ^２及びＲ^４がＨである。
（３）上記Ｎを含む１価の官能基が−Ｎ（Ｐｈ）_２である。
（４）Ｒ^１が３位においてヒドロキシル基であり、Ｒ^３が１１位においてヒドロキシル基であり、且つＲ^２及びＲ^４がＨである。
（５）Ｒ^１が３位においてメトキシ基であり、Ｒ^３が１１位においてメトキシ基であり、且つＲ^２及びＲ^４がＨである。
（６）Ｒ^１が３位においてトシル基であり、Ｒ^３が１１位においてトシル基であり、且つＲ^２及びＲ^４がＨである。 The compound of the present invention is a compound represented by the following formula (C1).

[In Formula (C1), R ^{1 to} R ⁴ each independently include a monovalent functional group containing H (hydrogen atom), X (halogen atom), or N (nitrogen atom), or O (oxygen atom). It is a monovalent functional group or a monovalent functional group containing S (sulfur atom). However, the case of any of (1) to (6) below is excluded. ]
(1) All of R ^{1 to} R ⁴ are H (hydrogen atom).
(2) R ¹ is Br at the 2-position, R ³ is Br at the 10-position, and R ² and R ⁴ are H.
(3) The monovalent functional group containing N is —N (Ph) ₂ .
(4) R ¹ is a hydroxyl group at the 3-position, R ³ is a hydroxyl group at the 11-position, and R ² and R ⁴ are H.
(5) R ¹ is a methoxy group at the 3-position, R ³ is a methoxy group at the 11-position, and R ² and R ⁴ are H.
(6) R ¹ is a tosyl group at the 3-position, R ³ is a tosyl group at the 11-position, and R ² and R ⁴ are H.

〔式（Ｃ１−１）中、Ｒ^１は、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕
この式（Ｃ１−１）において、上記Ｒ^１は１位、２位、３位及び４位のうちのいずれに置換されていてもよい。 In the above formula (C1), only one of R ^{1 to} R ⁴ is a substituent (a monovalent functional group containing X and N, a monovalent functional group containing O, or a monovalent functional group containing S) As the structure in which the other is a hydrogen atom, the following formula (C1-1) may be mentioned.

[In Formula (C1-1), R ¹ is a monovalent functional group containing X (halogen atom), N (nitrogen atom), a monovalent functional group containing O (oxygen atom), or S (sulfur atom ) Containing a monovalent functional group. ]
In the formula (C1-1), R ¹ may be substituted at any of the 1-position, 2-position, 3-position and 4-position.

〔式（Ｃ１−２）中、Ｒ^１及びＲ^２は、各々独立に、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕
この式（Ｃ１−２）において、Ｒ^１とＲ^２との置換位置の組合せとしては、［１，９］、［１，１０］、［１，１１］、［１，１２］、［２，９］、［２，１０］、［２，１１］、［２，１２］、［３，９］、［３，１０］、［３，１１］、［３，１２］、［４，９］、［４，１０］、［４，１１］、［４，１２］が挙げられる。 In the above formula (C1), two of R ^{1 to} R ⁴ are substituents (a monovalent functional group containing X and N, a monovalent functional group containing O, or a monovalent functional group containing S). In addition, examples of the structure in which the other is a hydrogen atom include the following formulas (C1-2), (C1-3), and (C1-4).

[In Formula (C1-2), R ¹ and R ² are each independently a monovalent functional group containing X (halogen atom) or N (nitrogen atom), or a monovalent functional group containing O (oxygen atom). Or a monovalent functional group containing S (sulfur atom). ]
In this formula (C1-2), combinations of substitution positions of R ¹ and R ² are [1,9], [1,10], [1,11], [1,12], [2, 9], [2, 10], [2, 11], [2, 12], [3, 9], [3, 10], [3, 11], [3, 12], [4, 9] , [4,10], [4,11], and [4,12].

〔式（Ｃ１−３）中、Ｒ^１及びＲ^２は、各々独立に、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕
この式（Ｃ１−３）において、Ｒ^１とＲ^２との置換位置の組合せとしては、［１，５］、［１，６］、［１，７］、［１，８］、［２，５］、［２，６］、［２，７］、［２，８］、［３，５］、［３，６］、［３，７］、［３，８］、［４，５］、［４，６］、［４，７］、［４，８］が挙げられる。

[In Formula (C1-3), R ¹ and R ² each independently represent a monovalent functional group containing X (halogen atom) or N (nitrogen atom), or a monovalent functional group containing O (oxygen atom). Or a monovalent functional group containing S (sulfur atom). ]
In this formula (C1-3), combinations of substitution positions of R ¹ and R ² are [1,5], [1,6], [1,7], [1,8], [2, 5], [2,6], [2,7], [2,8], [3,5], [3,6], [3,7], [3,8], [4,5] , [4,6], [4,7], [4,8].

〔式（Ｃ１−４）中、Ｒ^１及びＲ^２は、各々独立に、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕
この式（Ｃ１−４）において、Ｒ^１とＲ^２との置換位置の組合せとしては、［１，１３］、［１，１４］、［１，１５］、［１，１６］、［２，１３］、［２，１４］、［２，１５］、［２，１６］、［３，１３］、［３，１４］、［３，１５］、［３，１６］、［４，１３］、［４，１４］、［４，１５］、［４，１６］が挙げられる。

[In Formula (C1-4), R ¹ and R ² each independently represent a monovalent functional group containing X (halogen atom) or N (nitrogen atom), or a monovalent functional group containing O (oxygen atom). Or a monovalent functional group containing S (sulfur atom). ]
In this formula (C1-4), combinations of substitution positions of R ¹ and R ² are [1,13], [1,14], [1,15], [1,16], [2, 13], [2,14], [2,15], [2,16], [3,13], [3,14], [3,15], [3,16], [4,13] , [4,14], [4,15], and [4,16].

In these compounds of formula (C1-2) to formula (C1-4), R ¹ and R ² may be different substituents, but can be the same substituent. That is, both R ¹ and R ² can be halogen atoms. Moreover, both R ¹ and R ² can be a monovalent functional group containing N (nitrogen atom). Furthermore, both R ¹ and R ² can be a monovalent functional group containing O (oxygen atom). Further, both R ¹ and R ² can be a monovalent functional group containing S (sulfur atom).

〔式（Ｃ１−５）中、Ｒ^１、Ｒ^２及びＲ^３は、各々独立に、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕 In the above formula (C1), three of R ^{1 to} R ⁴ are substituents (a monovalent functional group containing X and N, a monovalent functional group containing O, or a monovalent functional group containing S). And as a structure whose others are a hydrogen atom, a following formula (C1-5) is mentioned.

[In formula (C1-5), R ¹ , R ² and R ³ each independently represent a monovalent functional group containing X (halogen atom) and N (nitrogen atom), and 1 containing O (oxygen atom). It is a monovalent functional group containing a valent functional group or S (sulfur atom). ]

In this formula (C1-5), combinations of substitution positions of R ^{1 to} R ³ are [1, 5, 9], [1, 5, 10], [1, 5, 11], [1, 5 , 12], [1, 6, 9], [1, 6, 10], [1, 6, 11], [1, 6, 12], [1, 7, 9], [1, 7, 10 ], [1, 7, 11], [1, 7, 12], [1, 8, 9], [1, 8, 10], [1, 8, 11], [1, 8, 12], [2, 5, 9], [2, 5, 10], [2, 5, 11], [2, 5, 12], [2, 6, 9], [2, 6, 10], [2 , 6, 11], [2, 6, 12], [2, 7, 9], [2, 7, 10], [2, 7, 11], [2, 7, 12], [2, 8 , 9], [2, 8, 10], [2, 8, 11], [2, 8, 12], [3, 5, 9], [3, 5, 10], [3 5, 11], [3, 5, 12], [3, 6, 9], [3, 6, 10], [3, 6, 11], [3, 6, 12], [3, 7, 9], [3, 7, 10], [3, 7, 11], [3, 7, 12], [3, 8, 9], [3, 8, 10], [3, 8, 11] , [3, 8, 12], [4, 5, 9], [4, 5, 10], [4, 5, 11], [4, 5, 12], [4, 6, 9], [ 4, 6, 10], [4, 6, 11], [4, 6, 12], [4, 7, 9], [4, 7, 10], [4, 7, 11], [4, 7,12], [4,8,9], [4,8,10], [4,8,11], [4,8,12].

In the compound of the formula (C1-5), R ^{1 to} R ³ may be different substituents, but can be the same substituent. That is, all of R ^{1 to} R ³ can be halogen atoms. Further, all of R ^{1 to} R ³ can be monovalent functional groups containing N (nitrogen atom). Furthermore, all of R ^{1 to} R ³ can be monovalent functional groups containing O (oxygen atom). Moreover, both R < ¹ > -R < ³ > can be a monovalent functional group containing S (sulfur atom).

〔式（Ｃ１−６）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々独立に、Ｘ（ハロゲン原子）、Ｎ（窒素原子）を含む１価の官能基、Ｏ（酸素原子）を含む１価の官能基、又はＳ（硫黄原子）を含む１価の官能基である。〕 In the above formula (C1), all ^four of R ^{1 to} R ⁴ are substituents (a monovalent functional group containing X and N, a monovalent functional group containing O, or a monovalent functional group containing S) As a structure which is), a following formula (C1-6) is mentioned.

[In formula (C1-6), R ¹ , R ² , R ³ and R ⁴ each independently represents a monovalent functional group containing X (halogen atom) or N (nitrogen atom), O (oxygen atom) Or a monovalent functional group containing S (sulfur atom). ]

In this formula (C1-6), combinations of substitution positions of R ^{1 to} R ⁴ are [3, 6, 11, 14], [3, 6, 11, 15], [3, 6, 10, 15 ], [2, 7, 10, 14], [2, 7, 10, 15], [3, 7, 10, 14], [3, 7, 11, 15], [3, 6, 10, 14 ], [3, 7, 10, 15], [3, 7, 11, 14], [2, 7, 11, 14], [2, 7, 11, 15], [2, 6, 10, 14 ], [2, 6, 10, 15], [2, 6, 11, 14], [2, 6, 11, 15], and the like.

In the compound of the formula (C1-6), R ^{1 to} R ⁴ may be different substituents, but can be the same substituent. That is, all of R ^{1 to} R ⁴ can be halogen atoms. Also, all of R ^{1 to} R ⁴ can be monovalent functional groups containing N (nitrogen atom). Furthermore, all of R ^{1 to} R ⁴ can be monovalent functional groups containing O (oxygen atom). Also, all of R ^{1 to} R ⁴ can be monovalent functional groups containing S (sulfur atom).

[1] X (Halogen Atom) in Formula (C1) Examples of X (halogen atom) in the above formula (C1) include Br, I, Cl and F. When any substituents of R ^{1 to} R ⁴ are X, R ^{1 to} R ⁴ may be different but are usually the same halogen atom.

That is, for example, as bromodibenzo [g, p] chrysene in which X (halogen atom) is Br, monobromodibenzo [g, p] chrysene {compound (C1-7)}, dibromodibenzo [g, p] chrysene {Compound (C1-8), Compound (C1-9) and Compound (C1-10)}, Tribromodibenzo [g, p] chrysene {Compound (C1-11)}, Tetrabromodibenzo [g, p] chrysene {Compound (C1-12)}.

In addition, as iododibenzo [g, p] chrysene in which X (halogen atom) is I, monoiododibenzo [g, p] chrysene {compound (C1-13)}, diiododibenzo [g, p] chrysene { Compound (C1-14), Compound (C1-15) and Compound (C1-16)}, triiododibenzo [g, p] chrysene {compound (C1-17)}, tetraiododibenzo [g, p] chrysene { Compound (C1-18)}.

  Halogenated dibenzo [g, p] chrysene compounds in which the hydrogen atoms constituting dibenzo [g, p] chrysene are substituted with X (halogen atoms) are useful as intermediates in the synthesis of various compounds. It is.

〔式（Ｃ４）のＲ^８は１価の有機基である。また、式（Ｃ５）のＲ^９及びＲ^１０は１価の有機基である。〕 [2] Monovalent functional group containing N in formula (C1) When R ^{1 to} R ⁴ in formula (C1) are monovalent functional groups containing N, the functional group may be dibenzo [ g, p] It is preferably a functional group in which N (nitrogen atom) is directly bonded to the carbon atom constituting the chrysene skeleton. Examples of the monovalent functional group containing N include a nitro group (—NO ₂ ), an amino group (—NH ₂ ), a diazo group (—N ₂ ⁺ ), and a functional group represented by the following formula (C4). And functional groups represented by the following formula (C5).

[R ^{8 in} Formula (C4) is a monovalent organic group. In addition, R ⁹ and R ¹⁰ in the formula (C5) are monovalent organic groups. ]

〔式（Ｃ６）のＲ^１１は、炭素数１〜３の直鎖又は分枝のアルキレン基である。〕 Examples of the organic group of R ^{8 to} R ^{10 in} the above formula (C4) and the above formula (C5) include a monovalent organic group having an epoxy terminal represented by the following formula (C6).

[R ^{11 in} Formula (C6) is a linear or branched alkylene group having 1 to 3 carbon atoms. ]

〔但し、式（Ｃ２）中のＲ^５及びＲ^６は、各々独立に、炭素数１〜３の直鎖又は分枝のアルキレン基である。〕 That is, the monovalent functional group containing N in the above formula (C1) includes a functional group represented by the following formula (C2).

[However, R ⁵ and R ⁶ in Formula (C2) are each independently a linear or branched alkylene group having 1 to 3 carbon atoms. ]

Accordingly, in the above formula (C1), as the nitrodibenzo [g, p] chrysene whose monovalent functional group containing N is a nitro group, mononitrodibenzo [g, p] chrysene {compound (C1-19)} Dinitrodibenzo [g, p] chrysene {compound (C1-20), compound (C1-21) and compound (C1-22)}, trinitrodibenzo [g, p] chrysene {compound (C1-23)}, And tetranitrodibenzo [g, p] chrysene {compound (C1-24)}.

  Nitrodibenzo [g, p] chrysene as described above is useful as an intermediate in the synthesis of various compounds, and particularly useful as an intermediate for obtaining aminodibenzo [g, p] chrysene described later. .

In addition, as the aminodibenzo [g, p] chrysene in which the monovalent functional group containing N in the above formula (C1) is an amino group, monoaminodibenzo [g, p] chrysene {compound (C1-25)} Diaminodibenzo [g, p] chrysene {compound (C1-26), compound (C1-27) and compound (C1-28)}, triaminodibenzo [g, p] chrysene {compound (C1-29)}, And tetraaminodibenzo [g, p] chrysene {compound (C1-30)}.

  The method for synthesizing these aminodibenzo [g, p] chrysene is not particularly limited. For example, as shown in the Examples, it can be obtained by reducing the nitro group of nitrodibenzo [g, p] chrysene to an amino group.

  The aminodibenzo [g, p] chrysene as described above is useful as an intermediate in the synthesis of various compounds, and in particular, hydroxyldibenzo [g, p] chrysene and glycidylaminodibenzo [g, p] described later. It is useful as an intermediate for obtaining compounds such as chrysene.

In addition, aminodibenzo [g, p] chrysene can be obtained from (1) monomer {especially compound (C1-26) to compound (C1-30)}, (2) curing agent {particularly compound (C1-25). ~ Compound (C1-30)}, (3) Crosslinker {particularly, Compound (C1-29) to Compound (C1-30)} are useful.
In particular, the monomer (1) can be used as a monomer for obtaining a polymer such as polyimide, polyamide, polyamideimide, polyetherimide, polyaminobismaleimide, or polyurea. That is, it can be used as a monomer for supplying an amino group such as a diamine monomer used in obtaining these polymers. Aminodibenzo [g, p] chrysene may be used alone as a monomer for supplying an amino group, or may be used in combination with another monomer for supplying an amino group. Examples of the monomer that supplies other amino groups include diamine monomers such as diaminobenzene and 4,4′-diaminodiphenyl ether in polyimide. Moreover, diamine monomers, such as hexamethylene diamine and phenylene diamine in polyamide, are mentioned.

  When aminodibenzo [g, p] chrysene is used as a monomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) can be introduced into the main chain of the polymer. For this reason, compared with the case where the conventional general purpose monomer is utilized, a glass transition point is high and high heat resistance can be obtained. Further, the thermal conductivity can be improved by stacking the dibenzo [g, p] chrysene skeletons. Furthermore, the dibenzo [g, p] chrysene skeleton having a large conjugated structure is a rigid molecule and has high heat resistance. Nevertheless, it exhibits a twisted structure and has a relatively high solubility in solvents and the like. For this reason, blending with other monomers is easy, and it is easy to control the properties of the resulting polymer. The dibenzo [g, p] chrysene skeleton has a twisted structure in which the carbon atoms at the 3-position, 6-position, 11-position and 14-position constituting this skeleton are not arranged in the same plane, and various optical isomers can be obtained. Have. For this reason, the toughness of the polymer obtained can be improved by using together the compound which has different optical activity from the said dibenzo [g, p] chrysene compound.

Further, in the above formula (C1), the monovalent functional group containing N has a diglycidylamino group {formula (C2) as an amino group containing an epoxy end, and R ⁵ and R ^{6 in} formula (C2) are The dibenzo [g, p] chrysene compound, which is a methylene group, is a dibenzo [g, p] chrysene {compound (C1-31)} having one diglycidylamino group and two diglycidyls. Dibenzo [g, p] chrysene having amino group {compound (C1-32), compound (C1-33) and compound (C1-34)}, dibenzo [g, p] chrysene having three diglycidylamino groups { Compound (C1-35)} and dibenzo [g, p] chrysene {compound (C1-36)} having four diglycidylamino groups.

  A method for synthesizing these dibenzo [g, p] chrysene compounds having a diglycidylamino group is not particularly limited. For example, as shown in Examples, the amino group of aminodibenzo [g, p] chrysene can be obtained by glycidylation.

The dibenzo [g, p] chrysene compound having a diglycidylamino group is composed of (1) monomer {particularly compound (C1-32) to compound (C1-36)}, (2) curing agent {particularly, Compound (C1-31)}, (3) Crosslinker {particularly, compound (C1-35) to compound (C1-36)} are useful.
Especially as said (1), it can utilize as a monomer (epoxy monomer) which supplies an epoxy terminal, an oligomer (epoxy oligomer) which supplies an epoxy terminal, etc. for obtaining an epoxy polymer. The dibenzo [g, p] chrysene compound having a diglycidylamino group may be used alone as an epoxy monomer or an epoxy oligomer, or may be used in combination with another epoxy monomer or an epoxy oligomer. Examples of other epoxy monomers and epoxy oligomers include bisphenol type epoxy oligomers, biphenyl type epoxy oligomers, naphthalene type epoxy oligomers, and fluorene type epoxy oligomers.

  When the dibenzo [g, p] chrysene compound having a diglycidylamino group is used as a monomer or oligomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) is added to the main chain of the epoxy resin. Can be introduced. For this reason, compared with the case where the conventional general purpose monomer and oligomer are utilized, a glass transition point is high and high heat resistance can be obtained. Further, the thermal conductivity can be improved by stacking the dibenzo [g, p] chrysene skeletons. Furthermore, the dibenzo [g, p] chrysene skeleton having a large conjugated structure is a rigid molecule and has high heat resistance. Nevertheless, it exhibits a twisted structure and has a relatively high solubility in solvents and the like. For this reason, blending with other monomers is easy, and it is easy to control the properties of the resulting polymer. The dibenzo [g, p] chrysene skeleton has a twisted structure in which the carbon atoms at the 3-position, 6-position, 11-position and 14-position constituting this skeleton are not arranged in the same plane, and various optical isomers can be obtained. Have. For this reason, the toughness of the polymer obtained can be improved by using together the compound which has different optical activity from the said dibenzo [g, p] chrysene compound.

〔式（Ｃ７）のＲ^１２は１価の有機基である〕 [3] Monovalent functional group containing O in formula (C1) When R ^{1 to} R ⁴ in formula (C1) are monovalent functional groups containing O, the functional group may be dibenzo [ g, p] A functional group in which O (oxygen atom) is directly bonded to a carbon atom constituting the chrysene skeleton is preferable. Examples of the monovalent functional group containing O include a hydroxyl group (—OH), a functional group represented by the following formula (C7), and the like.

[R ^{12 in} Formula (C7) is a monovalent organic group]

〔式（Ｃ６）のＲ^１１は、炭素数１〜３の直鎖又は分枝のアルキレン基である。〕 Examples of the organic group represented by R ¹² in the above formula (C7) include a monovalent organic group having an epoxy terminal represented by the following formula (C6).

[R ^{11 in} Formula (C6) is a linear or branched alkylene group having 1 to 3 carbon atoms. ]

〔式（Ｃ３）のＲ^７は、炭素数１〜３の直鎖又は分枝のアルキレン基である〕 That is, the monovalent functional group containing O in the above formula (C1) includes a functional group represented by the following formula (C3).

[R ^{7 in} Formula (C3) is a linear or branched alkylene group having 1 to 3 carbon atoms]

In the above formula (C1), as the hydroxyl dibenzo [g, p] chrysene whose monovalent functional group containing O is a hydroxyl group, monohydroxyl dibenzo [g, p] chrysene {compound (C1-37)}, dihydroxy Dibenzo [g, p] chrysene {compound (C1-38), compound (C1-39) and compound (C1-40)}, trihydroxydibenzo [g, p] chrysene {compound (C1-41)}, tetrahydroxy And dibenzo [g, p] chrysene {compound (C1-42)}.

  The method for synthesizing these hydroxyl dibenzo [g, p] chrysene is not particularly limited. For example, as shown in the Examples, (1) after obtaining a diazonium salt by diazotizing the amino group of aminodibenzo [g, p] chrysene, the resulting diazonium salt can be obtained by decomposition. Alternatively, (2) after dibenzo [g, p] chrysene is sulfonated, the obtained dibenzo [g, p] chrysenesulfonate can be hydroxylated.

The above hydroxyldibenzo [g, p] chrysene is: (1) monomer for polymer {particularly compound (C1-38) to compound (C1-42)}, (2) curing agent {particularly compound It is useful as (C1-37) to compound (C1-42)}, (3) cross-linking agent {particularly compound (C1-41) to compound (C1-42)} and the like.
In particular, when used as the monomer (1), for example, a monomer having an epoxy terminus (—C ₂ H ₃ O), a monomer having an amino terminus (—NH ₃ ), a carboxyl group terminus (— It can be copolymerized with other monomers such as monomers having (COOH). Other monomers may use only 1 type and may use 2 or more types together.
Specifically, it can be used as a monomer for obtaining a polymer such as polyester, polyether polymer (polyetherketone, etc.), polycarbonate, polyurethane and the like. Hydroxyl dibenzo [g, p] chrysene may be used alone as a monomer for supplying a hydroxyl group, or may be used in combination with another monomer for supplying a hydroxyl group.

  When the hydroxyl dibenzo [g, p] chrysene is used as a monomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) can be introduced into the main chain of the polymer. For this reason, compared with the case where the conventional general purpose monomer is utilized, a glass transition point is high and high heat resistance can be obtained. Further, the thermal conductivity can be improved by stacking the dibenzo [g, p] chrysene skeletons. Furthermore, the dibenzo [g, p] chrysene skeleton having a large conjugated structure is a rigid molecule and has high heat resistance. Nevertheless, it exhibits a twisted structure and has a relatively high solubility in solvents and the like. For this reason, blending with other monomers is easy, and it is easy to control the properties of the resulting polymer. The dibenzo [g, p] chrysene skeleton has a twisted structure in which the carbon atoms at the 3-position, 6-position, 11-position and 14-position constituting this skeleton are not arranged in the same plane, and various optical isomers can be obtained. Have. For this reason, the toughness of the polymer obtained can be improved by using together the compound which has different optical activity from the said dibenzo [g, p] chrysene compound.

In the above formula (C1), the monovalent functional group containing O has a glycidyl ether group {the formula (C3) as an ether group containing an epoxy terminal, and R ⁷ in the formula (C3) is a methylene group. The dibenzo [g, p] chrysene compound that is a functional group} is a dibenzo [g, p] chrysene {compound (C1-43)} having one glycidyl ether group and a dibenzo [g, p] chrysene {compound (C1-44), compound (C1-45) and compound (C1-46)}, dibenzo [g, p] chrysene {compound (C1-47)} having three glycidyl ether groups, 4 And dibenzo [g, p] chrysene {compound (C1-48)} having two glycidyl ether groups.

  The synthesis method of the dibenzo [g, p] chrysene compound having these glycidyl ether groups is not particularly limited. For example, as shown in Examples, the hydroxyl group of hydroxydibenzo [g, p] chrysene can be obtained by glycidylation.

The above-mentioned dibenzo [g, p] chrysene compound having a glycidyl ether group is: (1) monomer for polymer {particularly compound (C1-44) to compound (C1-48)}, (2) curing It is useful as an agent {particularly compound (C1-43) to compound (C1-48)}, (3) a crosslinking agent {particularly compound (C1-47) to compound (C1-48)}.
Especially as said (1), it can utilize as a monomer (epoxy monomer) which supplies an epoxy terminal, an oligomer (epoxy oligomer) which supplies an epoxy terminal, etc. for obtaining an epoxy polymer. The dibenzo [g, p] chrysene compound having a glycidyl ether group may be used alone as an epoxy monomer or an epoxy oligomer, or may be used in combination with other epoxy monomers or epoxy oligomers. Examples of other epoxy monomers and epoxy oligomers include bisphenol type epoxy oligomers, biphenyl type epoxy oligomers, naphthalene type epoxy oligomers, and fluorene type epoxy oligomers.

  When the dibenzo [g, p] chrysene compound having a glycidyl ether group is used as a monomer or oligomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) is introduced into the main chain of the epoxy resin. it can. For this reason, compared with the case where the conventional general purpose monomer and oligomer are utilized, a glass transition point is high and high heat resistance can be obtained. Further, the thermal conductivity can be improved by stacking the dibenzo [g, p] chrysene skeletons. Furthermore, the dibenzo [g, p] chrysene skeleton having a large conjugated structure is a rigid molecule and has high heat resistance. Nevertheless, it exhibits a twisted structure and has a relatively high solubility in solvents and the like. For this reason, blending with other monomers is easy, and it is easy to control the properties of the resulting polymer. The dibenzo [g, p] chrysene skeleton has a twisted structure in which the carbon atoms at the 3-position, 6-position, 11-position and 14-position constituting this skeleton are not arranged in the same plane, and various optical isomers can be obtained. Have. For this reason, the toughness of the polymer obtained can be improved by using together the compound which has different optical activity from the said dibenzo [g, p] chrysene compound.

[4] Monovalent functional group containing S in formula (C1) When R ^{1 to} R ⁴ in formula (C1) are monovalent functional groups containing S, the functional group may be dibenzo [ g, p] A functional group in which S (sulfur atom) is directly bonded to a carbon atom constituting the chrysene skeleton is preferable. Examples of such a monovalent functional group containing S include a thiol group (—SH).

As the dibenzo [g, p] chrysene compound in which the monovalent functional group containing S is a thiol group, the dibenzo [g, p] chrysene compound {compound (C1-49)} having one thiol group and two thiols Dibenzo [g, p] chrysene compound having a group {compound (C1-50), compound (C1-51) and compound (C1-52)}, a dibenzo [g, p] chrysene compound having three thiol groups {compound (C1-53)}, a dibenzo [g, p] chrysene compound {compound (C1-54)} having four thiol groups.

The synthesis method of the dibenzo [g, p] chrysene compound having these thiol groups is not particularly limited. For example, after sulfonating dibenzo [g, p] chrysene, the sulfonic acid group of the obtained compound is converted into a sulfonyl halogen group (—SO ₂ X), and the sulfonyl halogen group of the obtained compound is converted into a thiol group. (See Scheme S10). In addition, by making triphenylphosphine and iodine act on dibenzo [g, p] chrysenesulfonic acid in Scheme S10, the sulfonic acid group can be directly converted into a thiol group without using a sulfonyl halogen group. it can.

The dibenzo [g, p] chrysene compound having the above thiol group is: (1) monomer for polymer {particularly, compound (C1-50) to compound (C1-54)}, (2) curing agent {Especially useful as compound (C1-49) to compound (C1-54)}, (3) crosslinking agent {particularly compound (C1-53) to compound (C1-54)} and the like.
In particular, when used as a monomer, for example, a monomer having an epoxy terminal (—C ₂ H ₃ O), a monomer having an amino terminal (—NH ₃ ), and a carboxyl group terminal (—COOH) are used. It can be copolymerized with other monomers such as monomers. Other monomers may use only 1 type and may use 2 or more types together.

When a dibenzo [g, p] chrysene compound having the above thiol group is used as a monomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) can be introduced into the main chain of the polymer. This is the same as when hydroxyldibenzo [g, p] chrysene is used as a monomer. Also, the effect is the same as when hydroxyldibenzo [g, p] chrysene is used as a monomer.
In addition, a compound having a thiol group generally has an odor, but the dibenzo [g, p] chrysene compound having a thiol group has almost no odor. For this reason, it is useful for the utilization in the field | area where it is requested | required that it does not have an odor, such as a constituent material of household goods. In addition, as described above, the dibenzo [g, p] chrysene compound having a thiol group can be used as a monomer, a curing agent, and a crosslinking agent, and also as a synthesis raw material for synthesizing a photoacid generator. be able to.

〔式（Ｃ８）のＲ^１３は１価の有機基である〕 When R ^{1 to} R ⁴ in the above formula (C1) are monovalent functional groups containing S, examples of functional groups other than the thiol group (—SH) include functional groups represented by the following formula (C8) Is mentioned.

^{[R 13} of formula (C8) is a monovalent organic group]

〔式（Ｃ８１）のＲ^１４は、炭素数１〜３の直鎖又は分枝のアルキレン基である。〕 Examples of the organic group of R ¹³ in the above formula (C8) include a monovalent organic group having an epoxy terminal represented by the following formula (C81).

^{[R 14} of formula (C81) is a straight-chain or branched alkylene group having 1 to 3 carbon atoms. ]

〔式（Ｃ８２）のＲ^１５は、炭素数１〜３の直鎖又は分枝のアルキレン基である〕 That is, the monovalent functional group containing S in the above formula (C1) includes a functional group represented by the following formula (C82).

^{[R 15} of formula (C82) is a straight-chain or branched alkylene group having 1 to 3 carbon atoms]

As the above formula (C82), a glycidyl thioether group (—S—CH ₂ —C ₂ H ₃ O) in which R 15 is a methylene group (—CH ₂ —) can be mentioned.
As the dibenzo [g, p] chrysene compound in which the monovalent functional group containing S is a glycidyl thioether group, the dibenzo [g, p] chrysene {compound (C1-55)} having one glycidyl thioether group, 2 Dibenzo [g, p] chrysene having two glycidylthioether groups {compound (C1-56), compound (C1-57) and compound (C1-58)}, dibenzo [g, p] chrysene having three glycidylthioether groups {Compound (C1-59)} and dibenzo [g, p] chrysene {compound (C1-60)} having four glycidylthioether groups.

  A method for synthesizing these dibenzo [g, p] chrysene compounds having a glycidyl thioether group is not particularly limited. For example, it can be obtained by glycidylating a thiol group of a dibenzo [g, p] chrysene compound having a thiol group. Specifically, the thiol group can be glycidylated by the action of epichlorohydrin, similarly to the glycidylation of the hydroxyl group in <Example 8> described later.

The above-mentioned dibenzo [g, p] chrysene compound having a glycidyl thioether group includes (1) monomer for polymer {particularly, compound (C1-56) to compound (C1-60)}, and (2) curing. It is useful as an agent {particularly compound (C1-55) to compound (C1-60)}, (3) a crosslinking agent {particularly compound (C1-59) to compound (C1-60)} and the like.
Especially as said (1), it can utilize as a monomer (epoxy monomer) which supplies an epoxy terminal, an oligomer (epoxy oligomer) which supplies an epoxy terminal, etc. for obtaining an epoxy polymer. The dibenzo [g, p] chrysene compound having a glycidyl thioether group may be used as an epoxy monomer or an epoxy oligomer, or may be used in combination with another epoxy monomer or an epoxy oligomer. Examples of other epoxy monomers and epoxy oligomers include bisphenol type epoxy oligomers, biphenyl type epoxy oligomers, naphthalene type epoxy oligomers, and fluorene type epoxy oligomers.

When the dibenzo [g, p] chrysene compound having a glycidyl thioether group is used as a monomer or oligomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) is introduced into the main chain of the epoxy resin. What can be done is the same as when hydroxyldibenzo [g, p] chrysene is used as a monomer. Also, the effect is the same as when hydroxyldibenzo [g, p] chrysene is used as a monomer.
Furthermore, a dibenzo [g, p] chrysene compound having a glycidyl thioether group and a polymer (such as an oligomer) containing the dibenzo [g, p] chrysene compound as a monomer can be used particularly for an adhesive having excellent adhesion to metals.

R ^{1 to} R ⁴ in the above formula (C1) are monovalent functional groups containing S, and the functional group represented by the above formula (C8) includes R ³ in the above formula (C8), Examples include a monovalent group having a polymerizable unsaturated bond at the terminal (hereinafter, the monovalent group having a polymerizable unsaturated bond at the terminal is simply referred to as “polymerizable unsaturated group”). Although carbon number of this polymerizable unsaturated group is not specifically limited, Usually, it is C2-C12.

Specifically, using the compound (C1-49) to compound (C1-54), which are dibenzo [g, p] chrysene compounds having the above thiol group, using the thiol group that these compounds have, A polymerizable unsaturated group can be obtained.
Similarly, using compounds (C1-55) to (C1-60) which are dibenzo [g, p] chrysene compounds having a glycidyl thioether group, utilizing the glycidyl thioether group of these compounds, A polymerizable unsaturated group can be obtained.
Hereinafter, a method for obtaining a dibenzo [g, p] chrysene compound having a polymerizable unsaturated group using these compounds will be described.

A dibenzo [g, p] chrysene compound having a polymerizable unsaturated group is obtained by reacting a dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group with acryloyl halide. (See Scheme S11). In the scheme (S11), X—CO—CH═CH ₂ (where X is a halogen atom) represents acryloyl halide. An acryloyl halide can react with a thiol group to give an acryloyl group. Examples of the acryloyl halide include acryloyl chloride and acryloyl bromide. These may use only 1 type and may use 2 or more types together.

Similarly, even if methacryloyl halide is reacted with dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group, dibenzo [g, p] chrysene having a polymerizable unsaturated group A compound is obtained (see Scheme S12). In the scheme (S12), X—CO—C (CH ₃ ) ═CH ₂ (where X is a halogen atom) represents a methacryloyl halide. Methacryloyl halide can react with a thiol group to give a methacryloyl group. Examples of the methacryloyl halide include methacryloyl chloride and methacryloyl bromide. These may use only 1 type and may use 2 or more types together.

Further, dibenzo [g, p] chrysene having a polymerizable unsaturated group by reacting dibenzo [g, p] chrysene compound (C1-55) to compound (C1-60) having a glycidylthioether group with acrylic acid. A compound is obtained (see Scheme S13). _CH 2 = _CH-COOH in the scheme (S13) denotes acrylic acid. Acrylic acid can give an acryloyloxy group (—OCO—CH═CH ₂ ) after opening the epoxy ring of the glycidyl thioether group.

Similarly, dibenzo [g, p] having a polymerizable unsaturated group by reacting dibenzo [g, p] chrysene compound (C1-55) to compound (C1-60) having a glycidylthioether group with methacrylic acid. A chrysene compound is obtained (see Scheme S14). In the scheme _{(S14) CH 2 = C (} CH 3) -COOH represents methacrylic acid. Methacrylic acid can give a methacryloyloxy group {—OCO—C (CH ₃ ) ═CH ₂ } after opening the epoxy ring of the glycidyl thioether group.

Furthermore, dibenzo [g, p] chrysene having a polymerizable unsaturated group is obtained by reacting dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group with glycidyl acrylate. A compound is obtained (see Scheme S15). _{CH 2 = CH-CO-O} -CH 2 -C 2 H 3 O in the scheme (S15) represents a glycidyl acrylate. Glycidyl acrylate can react with a thiol group to give an acryloyl group.

Similarly, dibenzo [g, p] having a polymerizable unsaturated group even when glycidyl methacrylate is reacted with dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group. A chrysene compound is obtained (see Scheme S16). _{CH 2 = C (CH 3)} -CO-O-CH 2 -C 2 H 3 O in the scheme (S16) represents a glycidyl methacrylate. Glycidyl methacrylate can react with a thiol group to give a methacryloyl group.

In addition, halogenated propene (3-chloro-1-propene, 3-bromo-1-propene, etc.) is added to the dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group. By reacting, a dibenzo [g, p] chrysene compound having a polymerizable unsaturated group is obtained (see Scheme S17). In the scheme (S17), X—CH ₂ —CH═CH ₂ (where X is a halogen atom) represents a halogenated propene. The halogenated propene can give a 2-propenyl group (—CH ₂ —CH═CH ₂ ) to the thiol group.

Similarly, dibenzo [g, p] chrysene compound (C1-49) to compound (C1-54) having a thiol group are converted to halogenated methylpropene (3-chloro-2-methyl-1-propene, 3-bromo- Even if 2-methyl-1-propene or the like is reacted, a dibenzo [g, p] chrysene compound having a polymerizable unsaturated group can be obtained (see Scheme S18). In the scheme (S18), X—CH ₂ —C (CH ₃ ) ═CH ₂ (where X is a halogen atom) represents a halogenated methylpropene. The halogenated methylpropene can give a 2-methyl-2-propenyl group {—CH ₂ —C (CH ₃ ) ═CH ₂ } to the thiol group.

  The dibenzo [g, p] chrysene compound having a polymerizable unsaturated group obtained by the above schemes (S11) to (S18) is similar to the dibenzo [g, p] chrysene compound having a thiol group for the polymer. It is useful as a monomer, a curing agent, and a crosslinking agent. Further, when it is used as a monomer, it is possible to introduce a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) into the main chain of the polymer, and the effect of this can be obtained with respect to hydroxyl dibenzo [g, p It is the same as when chrysene is used as a monomer.

  Furthermore, a polymer using the dibenzo [g, p] chrysene compound having these polymerizable unsaturated groups as a monomer is particularly useful as an optical material. Such a polymer using a monomer having a thioether group (—S—) directly bonded to a dibenzo [g, p] chrysene skeleton is an ether directly bonded to the dibenzo [g, p] chrysene skeleton. As compared with a polymer using a monomer having a group (—O—), an optical material having a high refractive index can be obtained.

In the present specification, among the forms (1) to (6) excluded from the above formula (C1), —N (Ph) ₂ in (3) constitutes an amino group (—NH ₂ ). Means a diphenylamino group in which both of the two hydrogen atoms are substituted with a phenyl group (—C ₆ H ₅ ).

The polymer of the present invention is obtained by using the compound of the present invention.
When the compound having a dibenzo [g, p] chrysene skeleton of the present invention is used as a monomer, a conjugated condensed polycyclic structure (dibenzo [g, p] chrysene skeleton) is introduced into the main chain of the resulting polymer. it can. A polymer in which a dibenzo [g, p] chrysene skeleton is introduced can obtain a higher glass transition temperature than a polymer obtained using only conventional general-purpose monomers. That is, a polymer having high heat resistance can be obtained.
Moreover, since the polymer obtained has a stacking structure of dibenzo [g, p] chrysene skeletons, a polymer having excellent thermal conductivity can be obtained.
Furthermore, the polymer having a dibenzo [g, p] chrysene skeleton exhibits a twisted structure in which the carbon atoms at the 3-position, 6-position, 11-position and 14-position constituting the skeleton are not arranged in the same plane. Has optical isomers. For this reason, a polymer having high toughness can be obtained by using a compound having different optical activity from the compounds of the present invention having a dibenzo [g, p] chrysene skeleton.

The polymer of the present invention includes, among others, the dibenzo of the present invention containing the formula (C6) and / or the formula (81) [g. p] A polymer (copolymer) of a chrysene compound and a copolymerizable monomer having at least one group selected from an amino group, a hydroxyl group, and a carboxyl group.
That is, as the dibenzo [g, p] chrysene compound of the present invention containing the formula (C6) and / or the formula (81), the glycidyl terminal represented by the formula (C2), the formula (C3) and / or the formula (C82) is used. A group having Examples of the compound of the present invention having such a group include compounds represented by formula (C1-31) to formula (C1-36). Specifically, the compound 51, the compound 52, and the compound 53 shown in the Example mentioned later are illustrated. In addition, compounds represented by formula (C1-43) to formula (C1-48) can be given. Specifically, the compound 91 and the compound 92 shown in the Example mentioned later are illustrated. Furthermore, the compound shown to a formula (C1-55)-a formula (C1-60) is mentioned.

  On the other hand, examples of the copolymerizable monomer having at least one group selected from the above-mentioned amino group, hydroxyl group, and carboxyl group include curing agents for curing various epoxy resins. Among the compounds of the invention, compounds represented by formula (C1-25) to formula (C1-30) can be given. Specifically, the compound 41, the compound 42, the compound 43, and the compound 44 shown in the Example mentioned later are illustrated. In addition, compounds represented by formula (C1-37) to formula (C1-42) can be given. Specifically, the compound 71, the compound 72, the compound 73, and the compound 74 shown in the Example mentioned later are illustrated. Further, compounds represented by formula (C1-49) to formula (C1-54) can be given.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, dibenzo [g. p] Chrysene is simply referred to as “dibenzochrysene” or “DBC”.

Example 1 Production of Bromodibenzochrysene (Bromo Compound of DBC) The synthesis shown in the following scheme (S1) was carried out according to the following steps (1-1) to (1-4), and bromodibenzochrysene (bromo compound of DBC). )

  (1-1) In a 5 L four-necked flask equipped with a mechanical stirrer and a reflux condenser, DBC (compound 10) 30 g (0.0913 mol), chloroform 900 g (manufactured by Wako Pure Chemical Industries, Ltd.), And stirred at room temperature to dissolve DBC in chloroform. The DBC (molecular weight 328.41) is an in-house synthesized product, and its purity by HPLC analysis is 99.8%.

(1-2) The content of (1-1) is cooled to 2 ° C. using an ice-salt bath (−5 ° C.), and in that state, a 5% Br ₂ -CHCl ₃ solution (bromine in chloroform) ) 950g was dripped over 1 hour using the dripping pump (PTFE diaphragm pump). While continuing stirring, the reaction was monitored using HPLC analysis every hour after the completion of the dropwise addition, and the increase in dibromodibenzochrysene (compound 22) was less than the increase in tribromodibenzochrysene (compound 23). At that time, 620 g of 1N NaHSO ₃ aqueous solution (1 mol / L NaHSO ₃ aqueous solution) was added to stop the reaction.
The 5% Br ₂ -CHCl ₃ solution is a solution prepared in advance by dissolving bromine in chloroform (manufactured by Wako Pure Chemical Industries, Ltd.). 950 g of 5% Br ₂ -CHCl ₃ solution contains 49.6 g (0.311 mol) of bromine (molecular weight 158.91).

(1-3) After the operation of (1-2) above, 526.6 g of 9% NaHCO ₃ aqueous solution was added to neutralize the contents, and the obtained contents were washed with water three times. That is, 450 g of distilled water was added and stirred, the contents were transferred to a 5 L separatory funnel and allowed to stand, and then the separated aqueous phase was discarded. Next, 450 g of fresh distilled water was added to the organic phase left in the separatory funnel, and the aqueous phase was discarded after stirring and standing. Thereafter, the same operation was further performed once using 450 g of fresh distilled water to discard the aqueous phase and leave the organic phase. The solvent was removed from the organic phase by concentration under reduced pressure using an evaporator to obtain 43.3 g of a white solid (yield: 97%).

(1-4) As a result of subjecting the white solid obtained by the above operation (1-3) to liquid chromatography / mass spectrometry (hereinafter simply referred to as “LC / MS analysis”), monobromodibenzochrysene (Compound 21) Was 9.4%, dibromodibenzochrysene (compound 22) was 77%, tribromodibenzochrysene (compound 23) was 12%, and a mixture of bromodibenzochrysene (the bromo compound of DBC).
LC / MS analysis was performed using a liquid chromatograph mass spectrometer (manufactured by Agilent Technologies, model “6220 Accurate-Mass TOF LC / MS”). The same applies to the following LC / MS analysis.

Example 2 Production of Nitrodibenzochrysene (DBC Nitro Compound) Synthesis shown in the following scheme (S2) was performed according to the following steps (2-1) to (2-5) to obtain nitrodibenzochrysene.

  (2-1) In a 300 mL four-necked flask equipped with a mechanical stirrer and a reflux condenser, 6.67 g (0.0203 mol) of DBC (Compound 10) and 200 g of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) And stirred in a water bath (26 ° C.) to completely dissolve DBC in chloroform. DBC (molecular weight 328.41) is an in-house synthesized product, and its purity by HPLC analysis is 99.8%.

(2-2) Add 7.58 g of 67.5% aqueous HNO ₃ solution (aqueous nitric acid solution) (containing 0.0812 mol of HNO ₃ ) to the contents of (2-1) above at a temperature of 26 ° C. with a pipette. Added dropwise over a period of minutes. By this dropwise addition, the contents generated heat, and the liquid temperature rose to 28 ° C. Furthermore, the liquid color changed from slightly yellow to black brown in about 10 minutes after the completion of the dropping. Stirring is continued in a state where the temperature of the contents is 26 to 27 ° C., and after about 15 minutes from the end of the dropping, a yellow-orange solid starts to precipitate, and the precipitates increase with the lapse of time. Became a slurry.
In addition, as a result of subjecting the precipitate obtained by the operation of (2-2) to LC / MS analysis, mononitrodibenzochrysene (compound 31) is the main component, and formation of dinitrodibenzochrysene (compound 32) is Almost not recognized. From the viewpoint of synthesizing mononitrodibenzochrysene (compound 31), it is preferable to maintain the reaction system at 25 ° C. or lower.

(2-3) The water bath used in the above operation (2-2) was replaced with a hot water bath having a temperature of 65 ° C., and a reflux reaction (inner temperature 59 ° C.) was performed for 4 hours. In the contents, the yellow slurry particles become finer, the ratio of dinitrodibenzochrysene (compound 32) detected by LC / MS analysis increases, and the production of dinitrodibenzochrysene (compound 32) proceeds. confirmed. In order to promote the formation of this dinitrodibenzochrysene (compound 32), 1.89 g of 67.5% aqueous HNO ₃ solution (aqueous nitric acid solution) (containing 0.0203 mol of HNO ₃ ) was further added, and the reflux reaction was carried out for 1 hour. Continued and finished the reaction.

  (2-4) While stirring until the temperature of the content subjected to the above operation (2-3) is 25 ° C. with stirring, Solid-liquid separation was performed using 2 filter papers, and solid matter was taken out. Next, after washing with 50 g of methanol for the purpose of removing acid content from the obtained solid, it was dried for 12 hours under a reduced pressure of 60 ° C. and 10 mmHg, and 7 g of yellow powder (yield 82%) Got.

(2-5) As a result of subjecting the yellow powder obtained by the above operation (2-4) to LC / MS analysis, 1.0% of mononitrodibenzochrysene (compound 31) and dinitrodibenzochrysene (compound 32) Was a mixture of nitrodibenzochrysene (DBC nitro) containing 95% and trinitrodibenzochrysene (compound 33) 1.0%.
The mass spectrum of each compound is shown in FIG. 1 (Compound 31), FIG. 2 (Compound 32), and FIG. 3 (Compound 33). Furthermore, the mass spectrum of tetranitrodibenzochrysene (compound 34) detected in a trace amount from the mixture is shown in FIG. 4 (compound 34).

<Example 3> Production of aminodibenzochrysene (DBC amine) Synthesis shown in the following scheme (S3) was performed according to the following steps (3-1) to (3-4) to obtain aminodibenzochrysene.

  (3-1) Mixture 3 (compound 31, compound 32 and compound 33) of nitrodibenzochrysene obtained in (2-5) above was added to a 200 mL three-necked flask equipped with a magnetic stirrer and a reflux condenser. 2.0 g), 5% Pd / C (50% water-wet palladium on carbon) 0.2 g (in terms of dry mass) and tetrahydrofuran (THF) 30 g were charged and stirred in a hot water bath (65 ° C.). Then, the contents were heated to 60 ° C.

(3-2) The content of (3-1) above includes 2.382 g of an 80% hydrazine aqueous solution (liquid in which hydrazine monohydrate is dissolved in water) {0.0382 mol of hydrazine (NH ₂ NH ₂ ) ) Was dropped with a pipette over 5 minutes. By this dripping, the contents gradually changed from a yellow slurry state to a reddish brown liquid. At this time, generation of nitrogen gas and exotherm (reflux) were observed. Thereafter, in a state where the temperature of the contents was 63 ° C., refluxing was continued for 2 hours while stirring to complete the reaction.

  (3-3) It cooled until the temperature of the content which performed operation of said (3-2) became 35 degreeC. Then, for the purpose of removing Pd / C, Buchner funnel and No. Solid-liquid separation was performed at a temperature of about 30 ° C. using 5C filter paper and a small amount of radiolite (filter aid), and a reddish brown liquid was taken out. Next, this reddish brown solution was charged into a 100 mL three-necked flask equipped with a concentrator, and the volume (tetrahydrofuran) was reduced to about half while the pressure was reduced by an aspirator at an internal temperature of about 45 ° C., and concentrated. A reddish brown solution was obtained.

  Furthermore, for the purpose of reprecipitation, the reddish brown solution obtained up to the above (3-3) was dropped with a pipette into 120 g of distilled water stirred in a 300 mL capacity beaker at room temperature. By this dripping, a yellowish red solid was deposited. Stirring in the beaker was continued for 30 minutes and the contents were stopped. Solid-liquid separation was performed using 2 filter papers to obtain a yellow-orange solid. The obtained solid content was dried at a temperature of 60 ° C. and a reduced pressure of 10 mmHg for 12 hours to obtain 1.5 g of yellow-orange powder (yield 88%).

(3-4) As a result of subjecting the yellow-orange powder obtained by the above operation (3-3) to LC / MS analysis, 4.0% of monoaminodibenzochrysene (compound 41) and diaminodibenzochrysene (compound 42) ) Was a mixture of 94% aminodibenzochrysene.
Triaminodibenzochrysene with a large number of amino group substitutions is considered to be easily dissolved in the liquid phase (THF + water), while monoaminodibenzochrysene with a small number of amino group substitutions is in the liquid phase (THF + water). It is considered that the amount of dissolution is small. For this reason, it is considered that triaminodibenzochrysene eluted into the aqueous phase in the above operation (3-3).

The mass spectrum of each compound is shown in FIG. 5 (Compound 41) and FIG. 6 (Compound 42). Furthermore, the mass spectrum of triaminodibenzochrysene (compound 43) detected in a trace amount from the mixture is shown in FIG. 7 (compound 43), and the mass spectrum of tetraaminodibenzochrysene (compound 44) is shown in FIG. 8 (compound 44).

<Example 4> Production of glycidylaminodibenzochrysene (glycidylamine derivative of DBC) The synthesis shown in the following scheme (S4) was carried out according to the steps (4-1) to (4-3) below to obtain glycidylaminodibenzochrysene. It was.

  (4-1) Mixture 4 of aminodibenzochrysene obtained in (3-4) above (including compound 41 and compound 42) in a 300 mL four-necked flask equipped with a magnetic stirrer and a reflux condenser. While charging 10.85 g, 27 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and 67.2 g (0.726 mol) of epichlorohydrin (manufactured by Kanto Chemical Co., Ltd.), keeping the temperature warm using a hot water bath The reaction was carried out with stirring at an internal temperature of 80 ° C. for 6 hours. This changed the contents to a reddish brown solution.

(4-2) Next, the internal temperature was lowered to 60 ° C. while continuing stirring in a hot water bath, and then 10.67 g of 50% NaOH aqueous solution (sodium hydroxide aqueous solution) (containing 0.267 mol of NaOH) It dropped by the pipette over 5 hours with respect to the content of said (4-1). Thereafter, stirring was continued for 3 hours and stopped.
Next, after removing the solvent (ethanol + water) while reducing the pressure with an aspirator, 100 g of toluene was added to dissolve the contents, and the water was washed with 50 g of distilled water three times. The solvent was removed from the phase under a reduced pressure of 100 ° C. and 1 mmHg to obtain 12.1 g of reddish brown mass (68% yield).

(4-3) As a result of measuring the epoxy equivalent of the reddish brown mass obtained by the above operation (4-2) by the following method, the epoxy equivalent was 121 g / eq (yield 68%).
Furthermore, the mass spectrum of each compound is shown in FIG. 9 (Compound 51) and FIG. 10 (Compound 52). A mass spectrum of tris (diglycidylamino) dibenzochrysene (compound 53) detected in a trace amount from the mixture is shown in FIG. 11 (compound 53).

Example 5 Production of diazonium salt of dibenzochrysene The synthesis shown in the following scheme (S5) was carried out according to the following steps (5-1) to (5-2) to obtain a diazonium salt of dibenzochrysene.

(5-1) A mixture of aminodibenzochrysene 4 (compound 41 and compound 42) obtained in (3-4) above was added to a three-necked flask with a capacity of 100 mL equipped with a magnetic stirrer and shielded from light with aluminum foil. 1.0 g, 30 g of distilled water, and 1.61 g (0.156 mol) of 98% H ₂ SO ₄ (manufactured by Wako Pure Chemical Industries, Ltd.), stirred in an ice bath, Was cooled to 3 ° C.

(5-2) Next, 0.404 g (containing 5.86 × 10 ⁻³ mol) of sodium nitrite was used as a 40% NaNO ₂ aqueous solution (sodium nitrite aqueous solution), and the contents of (5-1) above were pipetted. On the other hand, it was dripped over 1 minute. The contents turned red by the dripping. Thereafter, stirring was continued for 2 hours with the internal temperature kept at 3 ° C. and stopped. As a content, a slurry containing a diazonium salt of dibenzochrysene, a reddish brown precipitate, was obtained.
Thereafter, 0.041 g (4.18 × 10 ⁻⁴ mol) of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the resulting slurry to decompose the nitrous acid component (the nitrous acid component using KI starch paper). Confirmed disappearance).

<Example 6> Production of hydroxydibenzochrysene (1)
Synthesis shown in the following scheme (S6) was performed according to the following steps (6-1) to (6-2) to obtain hydroxydibenzochrysene.

(6-1) Distilled water charged into a 200 mL three-necked flask equipped with a magnetic stirrer was stirred on a boiling water bath. The slurry (mixture 6) containing the diazonium salt of dibenzochrysene obtained up to the above (5-2) was added dropwise to this distilled water using a pipette. This dripping confirmed generation of nitrogen gas and solid precipitation due to decomposition of the diazonium salt. After dropping, the reaction was continued for 1 hour at an internal temperature of 100 ° C., and then the contents were cooled to an internal temperature of 25 ° C.
After that, Buchner Roth and No. Solid-liquid separation was performed using 2 filter papers, and solid matter was taken out. Next, after washing with distilled water for the purpose of removing acid content from the obtained solid, it was dried at a temperature of 70 ° C. and a reduced pressure of 10 mmHg for 12 hours to obtain 1 g of black gray powder (yield 99%). )

(6-2) As a result of subjecting the black gray powder obtained by the above operation (6-1) to LC / MS analysis, 30% of monohydroxydibenzochrysene (compound 71) and 30% of dihydroxydibenzochrysene (compound 72) 47% of the mixture of hydroxydibenzochrysene contained.
Furthermore, the mass spectrum of each compound is shown in FIG. 12 (Compound 71) and FIG. 13 (Compound 72). A mass spectrum of trihydroxydibenzochrysene (compound 73) detected in a trace amount from the mixture is shown in FIG. 14 (compound 73), and a mass spectrum of tetrahydroxydibenzochrysene (compound 74) is shown in FIG. 15 (compound 74).

<Example 7> Production of hydroxydibenzochrysene (2)
Dibenzochrysenesulfonic acid calcium salt (mixture 8) was obtained by synthesis shown in the following scheme (S7) using dibenzochrysene (compound 10). Further, hydroxydibenzochrysene (mixture 7 ′) was obtained by the synthesis shown in the following scheme (S8) using the obtained calcium dibenzochrysene sulfonate (mixture 8).
Hereinafter, each of (7-1) and (7-2) will be described in detail.

(7-1) Production of dibenzochrysene sulfonate calcium salt (7-11) In a 1 L four-necked flask equipped with a mechanical stirrer, 20 g (0.06 mol) of DBC (Compound 10) and 95% sulfuric acid ( 200 g (1.94 mol) manufactured by Wako Pure Chemical Industries, Ltd. was charged, and the mixture was allowed to react with stirring at an internal temperature of 80 ° C. for 2 hours while keeping the temperature in a hot water bath. As a result, the content became a uniform gray viscous liquid.
The DBC (molecular weight 328.41) is an in-house synthesized product, and its purity by HPLC analysis is 99.8%.

(7-12) While cooling the flask containing the contents obtained in (7-11) above in an ice bath, 400 g of distilled water was added. In addition, at the time of this addition, it added, maintaining internal temperature of 40 degrees C or less, measuring temperature so that internal temperature may not exceed 40 degreeC by heat_generation | fever.
Next, 154.4 g (2.08 mol) of powdered calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask to which the distilled water was added. In addition, at the time of this addition, addition was performed while maintaining the internal temperature of 45 ° C. or lower while measuring the temperature so that the internal temperature did not exceed 45 ° C. due to heat generation. By this addition, calcium sulfate was precipitated as a white solid, and the contents became a slurry. Moreover, the liquid property was alkaline.

  (7-13) The slurry obtained in (7-12) above was obtained from a stainless steel Buchner funnel and A filtrate (light yellow liquid) obtained by suction filtration using two filter papers was collected. Further, the solid residue (mainly calcium sulfate) was washed with 350 g of distilled water, and the washing liquid was also collected and concentrated under reduced pressure together with the filtrate together with the filtrate using a rotary evaporator. As a result, 36.5 g of dibenzochrysenesulfonic acid calcium salt which was a light yellow powdery solid was obtained (yield 82.7%). Based on the results of LC / MS analysis of hydroxydibenzochrysene described later in (7-2), 98% of the dibenzochrysenesulfonic acid calcium salt is a 4-substituted dibenzochrysene sulfonate (Compound 81), and the remainder is a 3-substituted dibenzo It is thought to be mixture 8 which is chrysene sulfonate.

(7-2) Production of hydroxydibenzochrysene (7-21) 14.0 g (0.212 mol) of 85% potassium hydroxide particles (manufactured by Wako Pure Chemical Industries, Ltd.) in a cylindrical container having a volume of 100 ml made of nickel It was charged and melted hot on a hot plate (400 ° C.). Subsequently, 4.0 g (0.0055 mol) of dibenzochrysene sulfonic acid calcium salt (mixture 8) obtained in (7-1) above was added. In this addition, the dibenzochrysene sulfonic acid calcium salt was charged into the above nickel cylindrical container over 30 minutes, and the reaction was promoted by stirring with a stainless steel spoon at the time of charging. Further, the stirring was continued for 30 minutes after the addition of the dibenzochrysenesulfonic acid calcium salt. As a result, a reddish brown viscous liquid was obtained.

(7-22) The reddish brown viscous liquid obtained in (7-22) above (the contents of the nickel cylindrical container) was poured into a 200 ml cup made of stainless steel while it was hot and solidified by cooling. . Subsequently, 40 g of distilled water was added to the stainless steel cup to dissolve the solid matter, thereby obtaining a reddish brown slightly turbid liquid.
Next, the reddish brown liquid is transferred to a 200 ml glass beaker, and 35% hydrochloric acid (Wako Pure Chemical Industries, Ltd.) is added to the contents containing a brown solid while stirring using a magnetic stirrer. Obtained. During the addition, the addition was continued until the pH of the contents reached pH 3 while measuring the pH with a pH meter. It was confirmed that the brown solid was precipitated at the time of neutralization.

  (7-23) Thereafter, 30 g of ethyl acetate (Wako Pure Chemical Industries, Ltd.) was added to the contents obtained up to (7-22) above and stirred to dissolve the brown solid. And after leaving the obtained liquid to separate into an organic phase and an aqueous phase, the organic phase was fractionated. The separated organic layer was composed of a glass funnel and a No. After filtering through 2 filter papers to remove insoluble matter, the solution was concentrated under reduced pressure using a rotary evaporator to obtain 1.6 g of a brown powdery solid (yield 73.9%). As a result of subjecting the brown powdery solid obtained by the above operation to LC / MS analysis, a mixture in which 98% of the brown powdered solid is 4-substituted hydroxydibenzochrysene (compound 74) and the remainder is trisubstituted hydroxydibenzochrysene 7 '.

(7-3) Effects of Example 7 As shown in Examples 1 to 3 and Example 6 above, a nitro group was introduced into DBC, and the introduced nitro group was reduced to an amino group. After diazotizing the amino group, the resulting diazonium salt can be decomposed to obtain hydroxy DBC. In this case, 2-substituted hydroxy DBC is the main component. On the other hand, in the method of Example 7, it can be seen that the number of steps can be reduced as compared with the previous method and that 4-substituted hydroxy DBC can be easily obtained as a main component. These methods can be properly used according to the purpose.

<Example 8> Production of dibenzochrysene glycidyl ether Using hydroxydibenzochrysene (mixture 7 ') obtained in Example 7 above, the synthesis shown in the following scheme (S9) was performed to obtain dibenzochrysene glycidyl ether (mixture 9). Obtained.

  (8-1) In a 50 mL four-necked flask equipped with a magnetic stirrer and a reflux condenser, 1.0 g (about 0.0255 mol) of hydroxydibenzochrysene (mixture 7 ′) obtained in Example 7 and , 10 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 g (0.324 mol) of epichlorohydrin (manufactured by Kanto Chemical Co., Ltd.) were added, and the temperature was kept at 40 ° C. while keeping the temperature in a water bath. Stir.

  (8-2) Next, stirring was continued in a hot water bath and the internal temperature was kept at 40 ° C., while the content obtained in (8-1) was added to 0.43 g (0 0.011 mol) was added over 2 hours. After completion of the addition, stirring was continued for 1 hour to obtain a brown heterogeneous solution. Thereafter, the solvent (ethanol and epichlorohydrin) was removed from the resulting brown heterogeneous solution while reducing the pressure with an aspirator. Next, 10 g of methyl isobutyl ketone (MIBK) was added to the contents from which the solvent had been removed and stirred. Insolubles were removed using two filter papers.

(8-3) Thereafter, the solvent was removed from the liquid from which the insoluble matter had been removed using a rotary evaporator at a temperature of 80 ° C. and a reduced pressure of 1 mmHg to obtain 1.4 g of a yellow oil (yield: 82.8%). Got. The yellow oil obtained by the above operation was subjected to LC / MS analysis. As a result, 98% of the yellow oil was 4-substituted dibenzochrysene glycidyl ether (Compound 91), and the remainder was 3-substituted dibenzochrysene glycidyl ether (Compound 92). ).
The mass spectrum of 4-substituted dibenzochrysene glycidyl ether (Compound 91) is shown in FIG. 16, and the mass spectrum of 3-substituted dibenzochrysene glycidyl ether (Compound 92) is shown in FIG.

<Example 9> Evaluation of epoxy resin (1) Preparation of cured epoxy resin Monomer for epoxy resin and curing agent for epoxy resin of <Example 9-1> to <Example 9-4> shown in Table 1 below. Cured epoxy resins were prepared in combination with and the thermal properties of these cured epoxy resins were measured.

<Example 9-1>
Using the glycidylaminodibenzochrycene (glycidylamino DBC, mixture of compounds 51-53) obtained in Example 4 as a monomer and diaminodiphenylmethane (DDM) as a curing agent, the reaction equivalent is 1: 1. The mixture was pulverized and mixed in a measuring mortar. Next, the obtained powder mixture was melt-mixed on an aluminum pan at a temperature of 150 ° C. Furthermore, after performing vacuum defoaming, it was maintained at 150 ° C. for 30 minutes and at 200 ° C. for 30 minutes to obtain a cured brown resin mass.

<Example 9-2>
Dibenzochrysene glycidyl ether obtained in Example 8 (DBC glycidyl ether, mixture of compound 91-compound 92) was used as a monomer, diaminodiphenylmethane (DDM) was used as a curing agent, and the reaction equivalent was 1: 1. Measured and mixed in a mortar. Then, it hardened | cured on the same conditions as Example 9-1, and obtained the pale yellow resin lump.

<Example 9-3>
The dibenzochrysene glycidyl ether (DBC glycidyl ether, mixture of compound 91-compound 92) obtained in Example 8 was used as a monomer, and the aminodibenzochrysene (amino DBC, compound 41-compound 44) obtained in Example 3 was used. ) Was used as a curing agent and weighed and mixed in a mortar so that the reaction equivalent was 1: 1. Then, it hardened | cured on the same conditions as Example 9-1, and obtained the pale yellow resin lump.

<Example 9-4>
The dibenzochrysene glycidyl ether (DBC glycidyl ether, mixture of compound 91-compound 92) obtained in Example 8 was used as a monomer, and the hydroxy dibenzochrysene (hydroxy DBC, compound 73-compound 74) obtained in Example 7 was used. ) Was used as a curing agent and weighed and mixed in a mortar so that the reaction equivalent was 1: 1. Then, it hardened | cured on the same conditions as Example 9-1, and obtained the pale yellow resin lump.

(2) Evaluation of Cured Epoxy Resin Each 3 mg of each cured epoxy resin obtained in <Example 9-1> to <Example 9-4> was weighed, and each was used as an aluminum crimp cell for DSC measurement. Filled. Then, using a differential scanning calorimeter (manufactured by Shimadzu Corporation, model “DSC-50”), the thermal characteristics were measured when heating from room temperature to 450 ° C. at a temperature rising rate of 10 ° C./min. FIG. 18 shows a multiplex chart obtained by multiplex display of the obtained DSC analysis chart.
From the results of FIG. 18, the cured epoxy resin of <Example 9-1> is at a temperature of 210.93 ° C., and the cured epoxy resin of <Example 9-2> is at a temperature of 335.98 ° C. The cured epoxy resin of 9-3> has a thermal characteristic change point at a temperature of 321.95 ° C., and the cured epoxy resin of Example 9-4 has a temperature of 368.24 ° C. and a temperature of 382.27 ° C. Admitted.

Among these, <Example 9-1>, <Example 9-2>, and <Example 9-3> show significant changes in thermal characteristics during the heating process until reaching the thermal decomposition peak in any chart. Since it is not shown, it is considered that the change point of the thermal characteristics is the thermal decomposition start temperature. That is, the thermal decomposition starting temperature is 210.93 ° C. in <Example 9-1>, 335.98 ° C. in <Example 9-2>, and 321.95 ° C. in <Example 9-3>. (See Table 1).
In addition, since the DSC chart of the cured epoxy resin of <Example 9-1> to <Example 9-3> does not show significant endothermic behavior capable of reading the glass transition point, the melting point, and the like, these In the cured epoxy resin, glass transition and melting may overlap the thermal decomposition initiation region or may be a cured product that does not exhibit glass transition and melting.

  On the other hand, in <Example 9-4>, an endothermic behavior starting from a temperature of 368.24 ° C. was observed, which is considered to be a glass transition point. That is, the glass transition point of <Example 9-4> is 368.24 ° C. Furthermore, since a thermal decomposition peak is observed after the endothermic behavior, the thermal decomposition starting temperature of <Example 9-4> is a temperature of 382.27 ° C.

(3) Effect of Example 9 The glass transition temperature of a cured epoxy resin obtained by curing a general bisphenol A type epoxy resin using diaminodiphenylmethane (DDM) as a curing agent is 170 ° C. or less. From this, the polymer of the present invention using the compound of the present invention as a monomer (<Example 9-1> to <Example 9-4>) is very much in comparison with an epoxy resin which is usually considered. It can be seen that it has high heat resistance.
In particular, the glass transition temperature exhibited by the cured epoxy resin shown in <Example 9-4> is as high as 368.2 ° C. This glass transition temperature is higher than the glass transition temperature of 350 ° C. exhibited by the naphthalene skeleton epoxy resin considered to have the highest heat resistance as the currently known epoxy resins. From this, it can be seen that the compound of the present invention exhibits remarkably excellent characteristics as a monomer and a curing agent for a heat-resistant resin. As a matter of course, the monomer and the curing agent can be variously changed and combined using the compound of the present invention.

Furthermore, from the results of the multiplex chart in FIG. 18, glycidylamino DBC, which is the monomer used in <Example 9-1>, is mainly composed of a disubstituted product, whereas <Example 9-2>. DBC glycidyl ether, which is a monomer used in the above, has a 4-substituted product as a main component. Due to this difference, it is considered that higher heat resistance is obtained when a dibenzochrysene compound having a larger number of substitutions is used.
Similarly, amino DBC, which is a curing agent used in <Example 9-3>, is mainly composed of a disubstituted product, whereas hydroxy DBC, which is a curing agent used in <Example 9-4>, is The main component is a 4-substituted product. Due to this difference, it is considered that higher heat resistance is obtained when a dibenzochrysene compound having a larger number of substitutions is used.

<Example 10> Production of dibenzochrysene compound having thiol group (10-1) Production of dibenzochrysene sulfonic acid In a 300 ml four-necked flask equipped with a mechanical stirrer, "Production of hydroxy dibenzochrysene" of Example 7 20 g (0.0276 mol) of the mixture 8 (dibenzochrysenesulfonic acid calcium salt, see scheme S7) obtained up to (7-13) in “(2)” and 80 g of ion-exchanged water were charged and dissolved at 80 ° C. Subsequently, after cooling to 25 ° C., 62.5 g (0.60 mol) of 35% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and further calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added until solid precipitation started. Added. After that, Buchner Roth and No. Solid-liquid separation was performed using 2 filter papers, and solid matter was taken out. Subsequently, it dried for 12 hours under the reduced pressure of 90 degreeC and 10 mmHg, and obtained 13.3g (yield 74%) of dibenzochrysenesulfonic acid which is white powder (refer scheme S19).

(10-2) Production of dibenzochrysene compound having sulfonyl chloride group 10 g (0.015 mol) of dibenzochrysene sulfonic acid obtained in (10-1) above was added to a 300 ml four-necked flask equipped with a mechanical stirrer. And 53.5 g (0.45 mol) of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 g of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.), while keeping warm using a hot water bath Stirring was performed at an internal temperature of 80 ° C. for 12 hours. Thereafter, excess thionyl chloride was distilled off under a reduced pressure of 20 mmHg. As a result, 9.8 g (yield 90%) of a dibenzochrysene compound having a sulfonyl chloride group as a brown solid was obtained (see Scheme S20).

(10-3) Production of dibenzochrysene compound having thiol group 5.5 g of dibenzochrysene compound having sulfonyl chloride group obtained in (10-2) above in a 500 ml four-necked flask equipped with a mechanical stirrer (0.0076 mol), 250 g of acetonitrile (manufactured by Kanto Chemical Co., Inc.) and 24.8 g (0.38 mol) of zinc powder (manufactured by Honjo Chemical Co., Ltd.) were charged. Next, 83.4 g (0.80 mol) of 35% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the flask over 2 hours while stirring using a water bath at an internal temperature of 40 ° C. Furthermore, stirring was continued for 8 hours at an internal temperature of 70 ° C. while keeping the temperature in a hot water bath. Then, after cooling the content to room temperature, the insoluble matter was removed by filtration to obtain a solution. Next, the resulting solution was concentrated under reduced pressure until half of the solution was obtained, and then 100 g of ion-exchanged water was added to precipitate a solid. After that, Buchner Roth and No. Solid-liquid separation was performed using 2 filter papers. As a result, 1.8 g (yield 53%) of a dibenzochrysene compound having a thiol group, which was a brown powdery solid, was obtained (see Scheme S21).

  (10-4) As a result of subjecting the brown powdery solid obtained by the above operation (10-3) to LC / MS analysis, the brown powdery solid was dibenzochrysene compound having four thiol groups (C1- 54) (exact mass: 456.0135) 98% by mass and a dibenzochrysene compound (C1-53) (exact mass: 244.0414) having three thiol groups as the balance.

<Example 11> Observation of hydroxyl group addition state in hydroxy DBC Among the mixture 7 '(hydroxydibenzochrysene) obtained up to Example 7 (7-23), 4-substituted hydroxydibenzochrysene (the main component) The number of hydroxyl groups added and the position of addition of the compound 74) were observed by the following method.

Using a Fourier transform nuclear magnetic resonance apparatus (FT-NMR apparatus: Bruker Biospin, model “AVANCE III-600 with Cryo Probe”), ¹ H-NMR and ¹³ C-NMR were measured and structural analysis was performed. . Further, FIG. 19 shows the obtained ¹ H-NMR chart, and FIG. 20 shows an enlarged chart of a part of FIG. Further, FIG. 21 shows a ¹³ C-NMR chart, and FIG. 22 shows a partially enlarged chart of FIG.
The measurement conditions in this FT-NMR measurement are as follows.
Observation frequency: ¹ H-NMR is 600 MHz, ¹³ C-NMR is 150 MHz
Measurement solvent: CDCl ₃ , DMSO-d ₆
Measurement temperature: 300K
Chemical shift criteria; CDCl ₃ ¹ H; 7.25 ppm, ¹³ C; 77.05 ppm
DMSO-d ₆ ¹ H; 2.50 ppm, ¹³ C; 39.50 ppm

The isomer separation of the compound 74 obtained in Example 7 was performed under the following conditions using a high performance liquid chromatograph (manufactured by Shimadzu Corporation, model “Prominence LC-20A”).
Column: manufactured by Intact Co., Ltd. Model “Cadenza CD-C18 4.6 × 150”, column temperature: 40 ° C., mobile phase: methanol (A) and 0.01% formic acid (B), gradient; A: B = 6: 4, flow rate; 1 mL / min, detector; UV254 nm.

As a result, from the integral curve of the ¹ H-NMR spectrum, the average number of hydroxyl groups added was determined to be 4 on the dibenzochrysene structure. That is, it was confirmed that the compound 74 was 4-substituted hydroxydibenzochrysene.
Furthermore, from the peak pattern of the ¹ H-NMR spectrum, it was found that the hydroxyl group was not added at the 1st, 2nd, 4th, 5th, 8th, 9th, 12th and 13th positions. It was. Therefore, in the compound 74, the addition position of the hydroxyl group is [3, 6, 11, 14], [3, 6, 11, 15], [3, 6, 10, 15], [2, 7, 10, 14]. ], [2,7,10,15], [3,7,10,14], [3,7,11,15] are confirmed to be a mixture of all or part of the seven isomers. It was.
Furthermore, from the chromatogram obtained, there were four peaks related to compound 74 (peak 1; retention time 4.425, peak 2; retention time 4.842, peak 3; retention time 5.062, peak 4; retention time. 5.419). From this, it was confirmed that the compound 74 was a mixture containing at least four or more of the seven isomers.

  In addition, in this invention, it can restrict to what is shown to said specific Example, It can be set as the Example variously changed within the range of this invention according to the objective and the use.

Claims (10)

A compound represented by the following formula (C1).

[In Formula (C1), R ^{1 to} R ⁴ each independently include a monovalent functional group containing H (hydrogen atom), X (halogen atom), or N (nitrogen atom), or O (oxygen atom). It is a monovalent functional group or a monovalent functional group containing S (sulfur atom). However, the case of any of (1) to (6) below is excluded. ]
(1) All of R ^{1 to} R ⁴ are H (hydrogen atom).
(2) R ¹ is Br at the 2-position, R ³ is Br at the 10-position, and R ² and R ⁴ are H.
(3) The monovalent functional group containing N is —N (Ph) ₂ .
(4) R ¹ is a hydroxyl group at the 3-position, R ³ is a hydroxyl group at the 11-position, and R ² and R ⁴ are H.
(5) R ¹ is a methoxy group at the 3-position, R ³ is a methoxy group at the 11-position, and R ² and R ⁴ are H.
(6) R ¹ is a tosyl group at the 3-position, R ³ is a tosyl group at the 11-position, and R ² and R ⁴ are H. 2. The compound according to claim 1, wherein at least one of R ^{1 to} R ⁴ is a monovalent functional group containing the N. 3. The compound according to claim ₂ , wherein the monovalent functional group containing N is —NH ₂ . The compound according to claim 2, wherein the monovalent functional group containing N is represented by the following formula (C2).

[In the formula (C2), R ⁵ and R ⁶ are each independently a linear or branched alkylene group having 1 to 3 carbon atoms. ] The compound according to claim 1, wherein at least one of R ^{1 to} R ⁴ is a monovalent functional group containing O.   The compound according to claim 5, wherein the monovalent functional group containing O is —OH. The compound according to claim 5, wherein the monovalent functional group containing O is represented by the following formula (C3).

[In the formula (C3), R ⁷ is a linear or branched alkylene group having 1 to 3 carbon atoms] The compound according to claim 1, wherein at least one of R ^{1 to} R ⁴ is a monovalent functional group containing S.   The compound according to claim 8, wherein the monovalent functional group containing S is -SH.   A polymer obtained by using the compound according to any one of claims 1 to 9.

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