TW201802144A - Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic dianhydride used in manufacture of polyimide - Google Patents

Abstract

The present invention relates to a polyimide precursor and a polyimide containing at least one type of repeating unit in which the structure derived from the tetracarboxylic acid component is a structure represented by any one of formulas (A-1) to (A-4) shown below. (In the formula, each of R1, R2 and R3 independently represents -CH2-, -CH2CH2-, or -CH=CH-.) (In the formula, R4 represents -CH2-, -CH2CH2-, or -CH=CH-.) (In the formula, each of R5 and R6 independently represents -CH2-, -CH2CH2-, or -CH=CH-.) (In the formula, R7 represents -CH2CH2- or -CH=CH-.).

Description

Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic dianhydride used for making polyimide

The present invention relates to a polyimide having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, a precursor thereof, and a tetracarboxylic dianhydride used in the production thereof.

In recent years, with the advent of a highly information-oriented society, the development of optical materials such as liquid crystal alignment films and protective films for color filters in the fields of display devices such as optical fibers and optical waveguides is progressing. Especially in the field of display devices, the development of lightweight and flexible plastic substrates that replace glass substrates, and the development of bendable or roundable displays are actively underway. Therefore, there is a need for optical materials with higher performance that can be used in such applications.

Aromatic polyfluorene imine is inherently colored yellow-brown due to the formation of intramolecular conjugates or charge transfer complexes. In order to suppress the coloring method, it has been proposed to introduce a fluorine atom into a molecule, impart flexibility to a main chain, introduce a bulky group as a side chain, and the like to hinder the formation and display of a conjugate or a charge transfer complex in the molecule. Method of transparency.

In addition, a method has also been proposed in which a semialicyclic or fully cycloaliphatic polyfluorene imine that does not form a charge transfer complex is theoretically made to exhibit transparency. In particular, an aromatic tetracarboxylic dianhydride is used as a tetracarboxylic acid component, an alicyclic diamine is used as a diamine component and the highly transparent semi-alicyclic polyfluorene imine, and the alicyclic tetracarboxylic dianhydride is used as a tetracarboxylic acid. Numerous proposals have been made for a highly transparent semialicyclic polyfluorene imine having a carboxylic acid component and an aromatic diamine as the diamine component.

For example, Patent Document 1 discloses that an alicyclic tetracarboxylic acid component having at least one aliphatic 6-membered ring in the chemical structure and no aromatic ring and a chemical structure having at least one amide bond and an aromatic ring in the chemical structure A semialicyclic polyfluorene imide precursor obtained from an aromatic diamine component, and a polyfluorene. Specifically, in the example of Patent Document 1, as for the alicyclic tetracarboxylic acid component, bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, decahydro- 1,4: 5,8-Dimethynaphthalene-2,3,6,7-tetracarboxylic dianhydride, etc. As the aromatic diamine component having a fluorene bond and an aromatic ring, 4,4 is used '-Diaminobenzimetidine and the like. In the example of Patent Document 1, as other diamine components, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-oxydiphenylamine, and the like are used.

In addition, Patent Document 2 discloses a method for producing a polyamic acid characterized by reacting a specific alicyclic tetracarboxylic dianhydride and a diamine in the presence of an inorganic salt as a catalyst. In addition, in Example 8 of Patent Document 2, the alicyclic tetracarboxylic dianhydride hexacyclic ring was made in the presence of calcium chloride as a catalyst [6.6.1.1 ^3,6 .1 ^{10 , 13} .0 ^2,7 .0 ^{9 , 14} ] Heptadecanyl-4,5,11,13-tetracarboxylic dianhydride is reacted with 4,4'-diaminodiphenyl ether to synthesize polyimide and then imidize to obtain Polyimide. However, in Patent Document Comparative Example 52, the catalyst system without the addition of the calcium-based hexacyclo ^{[6.6.1.1 3,6 .1 10, 13 .0} 2,7 .0 9, 14] heptadecane -4,5,11,13-tetracarboxylic dianhydride is reacted with 4,4'-diaminodiphenyl ether to synthesize polyfluorinated acid, and polyimide obtained by fluorimidization is obtained. Polyimide has a low η _inh and cannot be formed into a film.

For semi-alicyclic polyimide, Non-Patent Document 1 discloses a soluble alicyclic polyamine obtained from tricyclodecene tetracarboxylic dianhydride (the addition product of benzene and maleic anhydride) and diaminodiphenyl ether. Reciprocal relationship between mitigation transfer and strength properties in sulfonium imine. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/124664 [Patent Document 2] Japanese Patent Laid-Open No. 5-271409 [Non-Patent Document]

[Non-Patent Document 1] Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya, 1987, No. 5, p. 40

[Problems to be Solved by the Invention] An object of the present invention is to provide novel polyimide and its precursor having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient. Another object of the present invention is to provide a novel tetracarboxylic dianhydride used in the production of polyimide, and a method for producing the same. [Solution to the problem]

The present invention relates to the following items. 1. A polyimide precursor comprising at least one of the repeating units represented by the following chemical formula (1-1), and the total content of repeating units represented by the chemical formula (1-1) relative to all repeating units 50 mol% or more;

式中，A₁₁ 係下列化學式(A-1)表示之4價基、或下列化學式(A-2)表示之4價基，B₁₁ 係下列化學式(B-1)表示之2價基、或下列化學式(B-2)表示之2價基，X₁ 、X₂ 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷基矽基；[Chemical 1]

In the formula, A ₁₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₁₁ is a divalent group represented by the following chemical formula (B-1), or A divalent group represented by the following chemical formula (B-2), X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl silyl group having 3 to 9 carbon atoms;

式中，R₁ 、R₂ 、R₃ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 2]

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 3]

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，n₁ 表示0~3之整數、n₂ 表示0~3之整數；Y₁ 、Y₂ 、Y₃ 各自獨立地表示選自於由氫原子、甲基、三氟甲基構成之群組中之1種，Q₁ 、Q₂ 各自獨立地表示選自於由直接鍵結、或式：-NHCO-、-CONH-、-COO-、-OCO-表示之基構成之群組中之1種；[Chemical 4]

In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a member selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the groups, Q ₁ and Q ₂ each independently represent a member selected from the group consisting of a group represented by a direct bond, or a formula: -NHCO-, -CONH-, -COO-, -OCO- 1 species

式中，Y₄ 表示氫原子、或碳數1~4之烷基。[Chemical 5]

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

2. A polyimide precursor, comprising: at least one of the repeating units represented by the following chemical formula (1-2);

式中，A₁₂ 為下列化學式(A-3)表示之4價基、或下列化學式(A-4)表示之4價基，B₁₂ 為具有芳香族環或脂環結構之2價基，X₃ 、X₄ 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷基矽基；[Chemical 6]

In the formula, A ₁₂ is a tetravalent group represented by the following chemical formula (A-3) or a tetravalent group represented by the following chemical formula (A-4), B ₁₂ is a divalent group having an aromatic ring or an alicyclic structure, and X ₃ , X ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl silyl group having 3 to 9 carbon atoms;

式中，R₅ 、R₆ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 7]

In the formula, R ₅ and R ₆ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 3. 如2.之聚醯亞胺前驅體，其中，該化學式(1-2)表示之重複單元之合計含量相對於全部重複單元為50莫耳%以上。[Chemical 8]

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. 3. The polyfluorene imide precursor according to 2., wherein the total content of the repeating units represented by the chemical formula (1-2) is 50 mol% or more relative to the total repeating units.

4. A polyimide, characterized in that it comprises at least one of the repeating units represented by the following chemical formula (2-1), and the total content of the repeating units represented by the chemical formula (2-1) is 50 moles relative to all the repeating units. Ears above

式中，A₂₁ 為下列化學式(A-1)表示之4價基、或下列化學式(A-2)表示之4價基，B₂₁ 為下列化學式(B-1)表示之2價基、或下列化學式(B-2)表示之2價基；[Chemical 9]

In the formula, A ₂₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₂₁ is a divalent group represented by the following chemical formula (B-1), or Divalent group represented by the following chemical formula (B-2);

式中，R₁ 、R₂ 、R₃ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 10]

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 11]

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，n₁ 表示0~3之整數，n₂ 表示0~3之整數；Y₁ 、Y₂ 、Y₃ 各自獨立地表示選自於由氫原子、甲基、三氟甲基構成之群組中之1種，Q₁ 、Q₂ 各自獨立地表示選自於由直接鍵結、或式：-NHCO-、-CONH-、-COO-、-OCO-表示之基構成之群組中之1種；[Chemical 12]

In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a member selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the groups, Q ₁ and Q ₂ each independently represent a member selected from the group consisting of a group represented by a direct bond, or a formula: -NHCO-, -CONH-, -COO-, -OCO- 1 species

式中，Y₄ 表示氫原子、或碳數1~4之烷基。[Chemical 13]

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

5. A polyimide, characterized in that it comprises at least one of the repeating units represented by the following chemical formula (2-2);

式中，A₂₂ 為下列化學式(A-3)表示之4價基、或下列化學式(A-4)表示之4價基，B₂₂ 為具有芳香族環或脂環結構之2價基；[Chemical 14]

In the formula, A ₂₂ is a tetravalent group represented by the following chemical formula (A-3) or a tetravalent group represented by the following chemical formula (A-4), and B ₂₂ is a divalent group having an aromatic ring or an alicyclic structure;

式中，R₅ 、R₆ 各自獨立地為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 15]

In the formula, R ₅ and R ₆ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 6. 如5.之聚醯亞胺，其中，該化學式(2-2)表示之重複單元之合計含量相對於全部重複單元為50莫耳%以上。[Chemical 16]

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. 6. The polyfluorene imide of 5., wherein the total content of the repeating units represented by the chemical formula (2-2) is 50 mol% or more relative to all the repeating units.

7. A polyimide, obtained from a polyimide precursor according to any one of 1. to 3. 8. A film comprising a polyimide obtained from a polyimide precursor according to any one of 1. to 3. or a polyimide according to any one of 4. to 6. to make. 9. A varnish comprising a polyimide precursor according to any one of 1. to 3. or a polyimide according to any one of 4. to 6. 10. A polyimide film obtained by using a polyimide precursor according to any one of 1. to 3. or a polyimide varnish according to any one of 4. to 6. 11. A substrate for a display, a touch panel, or a solar cell, comprising: a polyimide obtained from a polyimide precursor according to any one of 1. to 3. Polyimide of any one of 4. to 6.

12. A tetracarboxylic dianhydride represented by the following chemical formula (M-1);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -。 13. 一種下列化學式(M-2)表示之四酯化合物；[Chemical 17]

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —. 13. A tetraester compound represented by the following chemical formula (M-2);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。 14. 一種下列化學式(M-3)表示之四酯化合物；[Chemical 18]

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms. . 14. A tetraester compound represented by the following chemical formula (M-3);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。[Chemical 19]

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms. .

15. A method for producing a tetracarboxylic dianhydride, comprising the following steps: (A) In the presence of a base, an olefin compound represented by the following chemical formula (MA-1) and an aliphatic sulfonium chloride or an aromatic sulfonium Chlorine reaction to obtain an olefin compound represented by the following chemical formula (MA-2);

式中，R₅ ’、R₆ ’各自獨立地為-CH₂ -、或-CH₂ CH₂ -；[Chemical 20]

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —;

式中，R₅ ’、R₆ ’之含意同前述，R為也可以有取代基之烷基或芳基； (B)使該化學式(M-A-2)表示之烯烴化合物於鈀觸媒與銅化合物存在下和醇化合物與一氧化碳反應，而獲得下列化學式(M-A-3)表示之四酯化合物；[Chemical 21]

In the formula, R ₅ ′ and R ₆ ′ have the same meanings as above, and R is an alkyl group or an aryl group which may have a substituent; (B) The olefin compound represented by the chemical formula (MA-2) is used in a palladium catalyst and copper In the presence of the compound, the alcohol compound is reacted with carbon monoxide to obtain a tetraester compound represented by the following chemical formula (MA-3);

式中，R₅ ’、R₆ ’、R之含意同前述，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基； (C)從該化學式(M-A-3)表示之四酯化合物獲得下列化學式(M-3)表示之四酯化合物；[Chemical 22]

In the formula, R ₅ ′, R ₆ ′, and R have the same meanings as above, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms; (C) From the chemical formula (MA- 3) Tetraester compound represented by the following formula: The tetraester compound represented by the following chemical formula (M-3) is obtained;

式中，R₅ ’、R₆ ’、R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 之含意同前述； (D)由該化學式(M-3)表示之四酯化合物之氧化反應獲得下列化學式(M-2)表示之四酯化合物；[Chemical 23]

In the formula, R ₅ ′, R ₆ ′, R ₁₁ , R ₁₂ , R ₁₃ , R _{14 have} the same meanings as above; (D) The oxidation reaction of the tetraester compound represented by the chemical formula (M-3) gives the following chemical formula ( M-2) tetraester compound;

式中，R₅ ’、R₆ ’、R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 之含意同前述； (E)使該化學式(M-2)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-1)表示之四羧酸二酐；[Chemical 24]

In the formula, R ₅ ′, R ₆ ′, R ₁₁ , R ₁₂ , R ₁₃ , R _{14 have} the same meanings as above; (E) The tetraester compound represented by the chemical formula (M-2) is present in the presence of an acid catalyst in Reaction in an organic solvent to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-1);

式中，R₅ ’、R₆ ’之含意同前述。[Chemical 25]

In the formula, R ₅ ′ and R ₆ ′ have the same meanings as described above.

16. A tetracarboxylic dianhydride represented by the following chemical formula (M-4);

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-。 17. 一種下列化學式(M-5)表示之四酯化合物；[Chemical 26]

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. 17. A tetraester compound represented by the following chemical formula (M-5);

式中，R₇ 為-CH₂ CH₂ -、或-CH＝CH-，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基。 18. 一種下列化學式(M-6)表示之二鹵代二羧酸酐；[Chemical 27]

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-, and R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbon atoms. 18. A dihalodicarboxylic anhydride represented by the following chemical formula (M-6);

式中，X₁₁ 、X₁₂ 各自獨立地表示-F、-Cl、-Br、或-I中之任一者。 19. 一種下列化學式(M-7)表示之二羧酸酐；[Chemical 28]

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I. 19. A dicarboxylic anhydride represented by the following chemical formula (M-7);

[Chemical 29]

20. A method for producing a tetracarboxylic dianhydride, comprising the following steps: (A) reacting a dicarboxylic anhydride represented by the following chemical formula (MB) with 1,3-butadiene to obtain the following chemical formula (M-7 ) Represented by dicarboxylic anhydride;

[Chemical 30]

(B)使該化學式(M-7)表示之二羧酸酐與二鹵化劑反應，而獲得下列化學式(M-6)表示之二鹵代二羧酸酐；[Chemical 31]

(B) reacting the dicarboxylic anhydride represented by the chemical formula (M-7) with a dihalogenating agent to obtain a dihalodicarboxylic anhydride represented by the following chemical formula (M-6);

式中，X₁₁ 、X₁₂ 各自獨立地表示-F、-Cl、-Br、或-I中之任一者； (C)使該化學式(M-6)表示之二鹵代二羧酸酐與馬來酸酐反應，而獲得下列化學式(M-4-1)表示之四羧酸二酐；[Chemical 32]

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I; (C) the dihalodicarboxylic anhydride represented by the chemical formula (M-6) and Maleic anhydride is reacted to obtain tetracarboxylic dianhydride represented by the following chemical formula (M-4-1);

(D)使該化學式(M-4-1)表示之四羧酸二酐於酸存在下與醇化合物反應而獲得下列化學式(M-5-1)表示之四酯化合物；[Chemical 33]

(D) reacting a tetracarboxylic dianhydride represented by the chemical formula (M-4-1) with an alcohol compound in the presence of an acid to obtain a tetraester compound represented by the following chemical formula (M-5-1);

式中，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基； (E)使該化學式(M-5-1)表示之四酯化合物於金屬觸媒存在下與氫反應而獲得下列化學式(M-5-2)表示之四酯化合物；[Chem 34]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbon atoms; (E) The tetraester compound represented by the chemical formula (M-5-1) is present in a metal catalyst And reacting with hydrogen to obtain a tetraester compound represented by the following chemical formula (M-5-2);

式中，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 之含意同前述； (F)使該化學式(M-5-2)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-4-2)表示之四羧酸二酐；[Chemical 35]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R _{24 have} the same meanings as above; (F) reacting the tetraester compound represented by the chemical formula (M-5-2) in an organic solvent in the presence of an acid catalyst to obtain Tetracarboxylic dianhydride represented by the following chemical formula (M-4-2);

。[Chemical 36]

.

21. A method for producing a tetracarboxylic dianhydride, comprising the following steps: (A) A diene compound represented by the following chemical formula (MC-1) is reacted with an acetylene compound represented by the following chemical formula (MC-2) to obtain A diester compound represented by the following chemical formula (MC-3);

式中，R₄ 為-CH₂ -、-CH₂ CH₂ -、或-CH＝CH-；[Chemical 37]

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

式中，R₃₁ 、R₃₂ 各自獨立地為碳數1~10之烷基、或苯基；[Chemical 38]

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group;

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述； (B)利用該化學式(M-C-3)表示之二酯化合物之氧化反應，獲得下列化學式(M-C-4)表示之二酯化合物；[Chemical 39]

In the formula, R ₄ , R ₃₁ and R _{32 have} the same meanings as above; (B) The oxidation reaction of the diester compound represented by the chemical formula (MC-3) is used to obtain the diester compound represented by the following chemical formula (MC-4);

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述； (C)使該化學式(M-C-4)表示之二酯化合物於鈀觸媒及銅化合物存在下和醇化合物與一氧化碳反應而獲得下列化學式(M-C-5)表示之四酯化合物；[Chemical 40]

In the formula, R ₄ , R ₃₁ and R _{32 have} the same meanings as above; (C) The diester compound represented by the chemical formula (MC-4) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain the following Tetraester compound represented by Chemical Formula (MC-5);

式中，R₄ 、R₃₁ 、R₃₂ 之含意同前述，R₃₃ 、R₃₄ 各自獨立地為碳數1~10之烷基； (D)使該化學式(M-C-5)表示之四酯化合物於酸觸媒存在下於有機溶劑中反應，獲得下列化學式(M-9)表示之四羧酸二酐；[Chemical 41]

In the formula, R ₄ , R ₃₁ , and R _{32 have} the same meanings as above, and R ₃₃ and R ₃₄ are each independently an alkyl group having 1 to 10 carbon atoms; (D) a tetraester compound represented by the chemical formula (MC-5) React in an organic solvent in the presence of an acid catalyst to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-9);

式中，R₄ 之含意同前述。 [發明之效果][Chemical 42]

In the formula, R _{4 has} the same meaning as described above. [Effect of the invention]

According to the present invention, a novel polyimide having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, a precursor thereof, and a novel tetracarboxylic acid diamine used in manufacturing them can be provided. Anhydride, and its manufacturing method.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are easy to form a fine circuit, and are suitable for use in a substrate for forming a display or the like. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are suitable for use in a substrate for a touch panel or a solar cell.

The polyfluorene imide precursor of the first aspect of the present invention (hereinafter also referred to as "polyfluorene imine precursor (1-1)") includes at least one of the repeating units represented by the aforementioned chemical formula (1-1). 1 type, and the total content of repeating units represented by the chemical formula (1-1) is 50 mol% or more of a polyimide precursor. However, the aforementioned chemical formula (1-1) indicates that one of the four atomic bonds of the tetravalent group A ₁₁ derived from the tetracarboxylic acid component is bonded to -CONH-, and one is bonded to -CONH-B _11- , One is bonded to -COOX ₁ and one is bonded to -COOX ₂ , and the aforementioned chemical formula (1-1) includes all of its structural isomers.

The polyfluorene imide precursor (1-1) of the present invention is preferably one or more repeating units represented by the aforementioned chemical formula (1-1), and the total repeating units account for more than 50 mol%, and more preferably 60 mol. % Or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more.

Moreover, the polyfluorene imide precursor (1-1) of the present invention may contain two or more kinds of repeating units of the aforementioned chemical formula (1-1) different from A ₁₁ and / or B ₁₁ . In addition, the polyfluorene imide precursor (1-1) of the present invention may contain one of the repeating units of the aforementioned chemical formula (1-1) having a tetravalent group represented by A ₁₁ based on the aforementioned chemical formula (A-1). Or two or more of the repeating units of the aforementioned chemical formula (1-1) having a tetravalent group represented by the aforementioned chemical formula (A-2) of A ₁₁ is one or two or more.

In other words, the polyfluorene imide precursor (1-1) of the present invention is composed of a tetracarboxylic acid component provided with the structure of the aforementioned chemical formula (A-1) and / or Polytetracarboxylic acid component of a carboxylic acid component, and a polymer obtained by including a diamine component imparted to the structure of the aforementioned chemical formula (B-1) and / or a diamine component imparted to the diamine component of the structure of the aforementioned chemical formula (B-2) Imine precursor.

The tetracarboxylic acid component given to the repeating unit of the aforementioned chemical formula (1-1) is a tetracarboxylic acid component given to the structure of the aforementioned chemical formula (A-1) and a tetracarboxylic acid component given to the structure of the aforementioned chemical formula (A-2) . The tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-1) is given, for example: tetradecyl-1H, 3H-4,12: 5,11: 6,10-trimethyl bridge anthracene [2,3-c: 6 , 7-c '] difuran-1,3,7,9-tetraone, tetradecahydro-1H, 3H-4,12-ethyl bridge-5,11: 6,10-dimethyl bridge anthracene [2 , 3-c: 6,7-c '] difuran-1,3,7,9-tetraketone, tetradecahydro-1H, 3H-4,12: 5,11-diethyl bridge-6,10- Methylanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, tetradecahydro-1H, 3H-4,12: 5,11: 6, 10-trimethyl bridge anthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraketone, tetradecahydro-1H, 3H-5,11-ethyl bridge-4 , 12: 6,10-dimethylmethanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, tetradehydro-1H, 3H-4, 12-Ethylene Bridge-5,11: 6,10-Dimethylbridge Anthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, tetradehydro- 1H, 3H-4,12: 5,11-diethylene bridge-6,10-methanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetra Ketone, tetradecyl-1H, 3H-4,12: 5,11: 6,10-triethylene bridge anthracene [2,3-c: 6,7-c '] difuran-1,3,7, 9-tetraketone, tetradecahydro-1H, 3H-5,11-ethylene bridge-4,12: 6,10-dimethyl bridge anthracene [2,3-c: 6,7-c '] difuran- 1,3,7,9-tetraketone, and corresponding tetracarboxylic acid, tetracarboxylic acid di A tetracarboxylic acid derivative other than the tetracarboxylic acid derivative is given a tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-2), for example: 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-methanonaphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone, 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-ethyl bridgenaphthalene Benzo [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone, 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-ethylene bridge Naphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone, and corresponding tetracarboxylic acids, tetracarboxylic acid derivatives other than tetracarboxylic dianhydrides, etc. . These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used individually by 1 type, and may be used in combination of multiple types. Here, tetracarboxylic acids and the like represent tetracarboxylic acid derivatives such as tetracarboxylic acid, tetracarboxylic dianhydride, silicon tetracarboxylic acid ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.

The diamine component given to the repeating unit of the aforementioned chemical formula (1-1) is a diamine component given to the structure of the aforementioned chemical formula (B-1) and a diamine component given to the structure of the aforementioned chemical formula (B-2).

When the diamine component having the structure of the aforementioned chemical formula (B-1) is provided with an aromatic ring and a plurality of aromatic rings, the aromatic rings are each independently directly bonded to each other by a amine bond or an ester bond. The position where the aromatic rings are connected to each other is not particularly limited, and it is preferable to bond at the 4-position with respect to the amine group or the connecting group between the aromatic rings. That group, the aforementioned chemical formula (B-1) represented in the aromatic ring of another coupling position is not particularly limited with respect to the acyl group (-CONH-) A ₁₁ are bonded to each other or an aromatic ring of the linking group to 4-position bonding is preferred. By bonding in this way, the obtained polyimide becomes a linear structure, and the linear thermal expansion may become low. When the diamine component given the structure of the aforementioned chemical formula (B-1) has an aromatic ring, it is preferable to have a p-phenylene structure. That is, when the group represented by the aforementioned chemical formula (B-1) has one aromatic ring (when n ₁ and n ₂ are 0), the group represented by the aforementioned chemical formula (B-1) may have a substituent (Y ₁ ). The p-phenylene group is preferably an unsubstituted p-phenylene group. The aromatic ring may be substituted by a methyl group or a trifluoromethyl group. In addition, there is no particular restriction on the replacement position.

The diamine component given the structure of the aforementioned chemical formula (B-2) is a 6-membered aliphatic ring, and the 6-membered aliphatic ring can also be passed through methyl, ethyl, n-propyl, isopropyl, and n-butyl groups. , Isobutyl, second butyl, third butyl and other alkyl groups with 1 to 4 carbon atoms, but considering the heat resistance and linear thermal expansion coefficient of the obtained polyimide, the unsubstituted aliphatic 6-membered ring good. That is, in the group represented by the aforementioned chemical formula (B-2), Y _{4 is} preferably a hydrogen atom. In addition, there is no particular restriction on the replacement position. Furthermore, it is preferred that the diamine component having the structure of the aforementioned chemical formula (B-2) has a 1,4-cyclohexane structure in terms of an aliphatic 6-membered ring. That is, the base system represented by the aforementioned chemical formula (B-2) may have a 1,4-cyclohexyl group having a substituent (Y ₄ ), preferably an unsubstituted 1,4-cyclohexyl group.

The diamine component given the structure of the aforementioned chemical formula (B-1) is not particularly limited, for example: p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamine-biphenyl, 2,2'- Bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, m-toluidine, 4,4'-diaminobenzidine, 3,4'-diamine Phenylbenzidine, N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-p-phenylene bis (p-aminobenzidine), 4-amine Phenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid bis (4-aminophenyl) ) Ester, p-phenylene bis (p-aminobenzoate), bis (4-aminophenyl)-[1,1'-biphenyl] -4,4'-dicarboxylic acid ester, [1 , 1'-biphenyl] -4,4'-diylbis (4-aminobenzoate) and the like. Examples of the diamine component imparted to the structure of the aforementioned chemical formula (B-2) include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, and 1,4-diamine. 2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino 2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-second butylcyclohexane, 1,4-di Amino-2-third butylcyclohexane, 1,2-diaminocyclohexane, and the like. Given the diamine component of the structure of the aforementioned chemical formula (B-2), considering the viewpoint that the obtained polyimide has a low coefficient of thermal expansion, the 1,4-diaminocyclohexane is more preferable. In addition, the three-dimensional structure of the 1,4-position of the above-mentioned diamine having a 1,4-cyclohexane structure is not particularly limited, and a trans-structure is preferred. In the case of the trans structure, the obtained polyimide may be more inhibited from coloring than the cis structure. These diamine components may be used singly or in combination.

B ₁₁ in the aforementioned chemical formula (1-1), that is, the divalent group represented by the aforementioned chemical formula (B-1) and the divalent group represented by the aforementioned chemical formula (B-2), are preferably the following chemical formula (B-1- 1) A base represented by any of (B-1-6) and (B-2-1) is preferred.

[Chemical 43]

The diamine component of the repeating unit of the chemical formula (1-1) represented by B ₁₁ is represented by the aforementioned chemical formula (B-1-1) or (B-1-2) is a 4,4'-diamine group. Bentamidine, given to B ₁₁ is a diamine component of the repeating unit of the aforementioned formula (1-1) represented by the aforementioned formula (B-1-3), and is a bis (4-aminophenyl) p-xylylene Acid ester, to which B ₁₁ is the diamine component of the repeating unit of the aforementioned chemical formula (1-1) represented by the aforementioned chemical formula (B-1-4), is p-phenylenediamine, and B ₁₁ is the aforementioned chemical formula (B-1) -5) The diamine component of the repeating unit of the aforementioned chemical formula (1-1) is 2,2'-bis (trifluoromethyl) benzidine, and B ₁₁ is given by the aforementioned chemical formula (B-1-6) The diamine component of the repeating unit of the aforementioned chemical formula (1-1), m-toluidine, is given to the B ₁₁ series of the repeating unit of the aforementioned chemical formula (1-1). The diamine component is 1,4-diaminocyclohexane.

In B ₁₁ in the aforementioned chemical formula (1-1), the ratio of the bases represented by any one of the aforementioned chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is compared. It is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more.

The polyfluorene imide precursor (1-1) of the present invention may contain a repeating unit other than the repeating unit represented by the aforementioned chemical formula (1-1). In an embodiment, the repeating unit other than the repeating unit represented by the aforementioned chemical formula (1-1), such as a tetravalent group of a tetracarboxylic acid component, is a tetravalent group represented by the aforementioned chemical formula (A-1) or the aforementioned chemical formula The content of the repeating unit of the tetravalent group represented by (A-2) and the repeating unit of the divalent component derived from the diamine component having multiple aromatic rings and the aromatic rings connected with each other by an ether bond (-O-) in all the repeating units For example: 30 mol% or less, or 25 mol% or less, or 20 mol% or less, or 10 mol% or less is preferred. In an embodiment, the tetravalent group derived from the tetracarboxylic acid component is a tetravalent group represented by the aforementioned chemical formula (A-1) or a tetravalent group represented by the aforementioned chemical formula (A-2) depending on the required characteristics and applications. The divalent group derived from the diamine component is a repeating unit having a plurality of aromatic rings and the aromatic rings are connected by an ether bond (-O-). The content of the repeating units in all repeating units is, for example, 40 mol% or less, preferably 35 mol% or less is preferred.

As the tetracarboxylic acid component for giving other repeating units, aromatic or aliphatic tetracarboxylic acids can be used. Although there are no special restrictions, for example: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid Acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) pyrene dihydrate, intermoletris Benzene-3,4,3 ', 4'-tetracarboxylic dianhydride, terphenyltriphenyl-3,4,3', 4'-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxyl Phenoxy diphenyl sulfide, sulfofluorenyl diphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane -1,2,4,5-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-3,3 ', 4,4'-tetracarboxylic acid, [1,1'-bi (cyclic Hexane)]-2,3,3 ', 4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4 '-Methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfofluorene Bis (cyclohexane -1,2-dicarboxylic acid), 4,4 '-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2, 2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), octahydropentadiene-1,3,4,6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2,3 , 5,6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid, bicyclo [2.2.2] octane-2,3,5, 6-tetracarboxylic acid, bicyclic [2.2.2] oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclic [4.2.2.02,5] decane-3,4,7,8- Tetracarboxylic acid, tricyclic [4.2.2.02,5] dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3,4 , 7,8-tetracarboxylic acid, decahydro-1,4: 5,8-dimethyl bridgenaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone -α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid, and other dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used individually by 1 type, and may be used in combination of multiple types. Among these, bicyclic [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic acid, decahydro- 1,4: 5,8-Dimethynaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbidine Derivatives such as alkane-5,5 '', 6,6 ''-tetracarboxylic acid, and such acid dianhydrides are preferred.

When the combined diamine component is a diamine component given the structure of the aforementioned chemical formula (B-1) and a diamine other than the diamine component given the structure of the aforementioned chemical formula (B-2), other repeating units are given. As the tetracarboxylic acid component, one or two or more of the tetracarboxylic acid component given the structure of the aforementioned chemical formula (A-1) and the tetracarboxylic acid component given the structure of the aforementioned chemical formula (A-2) can be used.

As for the diamine component to which other repeating units are given, other aromatic or aliphatic diamines may be used. Although not particularly limited, for example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, bis (4-aminophenyl) sulfide, p -Methylenebis (phenylenediamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4 -Aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenyl) fluorene, 3,3-bis ((aminophenoxy) phenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, Bis (4- (4-aminophenoxy) diphenyl) fluorene, bis (4- (3-aminophenoxy) diphenyl) fluorene, octafluorobenzidine, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl Benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) Biphenyl, etc. and their derivatives. These diamine components may be used singly or in combination.

When the combined tetracarboxylic acid component is a tetracarboxylic acid component given a structure of the aforementioned chemical formula (A-1) and a tetracarboxylic acid component other than the tetracarboxylic acid component given a structure of the aforementioned chemical formula (A-2), For the diamine component given to other repeating units, one or two of the diamine component given to the structure of the aforementioned chemical formula (B-1) and the diamine component given to the structure of the aforementioned chemical formula (B-2) may be used. the above.

In a certain embodiment, for example, 4,4'-oxydiphenylamine, 4,4'-bis (4-aminophenoxy) biphenyl, and the like have multiple aromatic rings and the aromatic rings are ether-bonded (- O-) The content of the linked diamine component in 100 mol% of the diamine component is preferably, for example: 30 mol% or less, or 25 mol% or less, or 20 mol% or less, or 10 mol% or less Better. In a certain embodiment, depending on the required characteristics and applications, the amount of the diamine component having a plurality of aromatic rings and the aromatic rings connected with each other by an ether bond (-O-) is 100 mol% of the diamine component. It is preferably, for example, 40 mol% or less, more preferably 35 mol% or less.

The polyfluorene imide precursor of the second aspect of the present invention (hereinafter also referred to as "polyfluorene imide precursor (1-2)") contains at least one of the repeating units represented by the aforementioned chemical formula (1-2). A polyimide precursor. However, the aforementioned chemical formula (1-2) represents the four atomic bonds of the tetravalent group A ₁₂ derived from the tetracarboxylic acid component, one is bonded to -CONH-, and one is bonded to -CONH-B _12- , One is bonded to -COOX ₃ and one is bonded to -COOX ₄ , and the aforementioned chemical formula (1-2) includes all of its structural isomers.

The total content of the repeating units represented by the chemical formula (1-2) is not particularly limited, but it is preferably 50 mol% or more with respect to all the repeating units. That is, the polyfluorene imide precursor (1-2) of the present invention is more than 50 mol% in total of the repeating units represented by the aforementioned chemical formula (1-2). It is more preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more.

Moreover, the polyfluorene imide precursor (1-2) of the present invention may contain two or more kinds of repeating units of the aforementioned chemical formula (1-2) different from A ₁₂ and / or B ₁₂ . Further, the polyimide precursor of the present invention (1-2), A ₁₂ may contain repeat units (A-3) represents a tetravalent group of the chemical formula of the chemical formula (1-2) of one or two The above-mentioned repeating unit of the aforementioned chemical formula (1-2) having a tetravalent group represented by the aforementioned chemical formula (A-4) is more than A ₁₂ .

In other words, the polyimide precursor (1-2) of the present invention is composed of the tetracarboxylic acid component containing the structure given to the aforementioned chemical formula (A-3) and / or the fourth structure given to the aforementioned chemical formula (A-4) A tetracarboxylic acid component of a carboxylic acid component, and a polyimide precursor obtained from a diamine component containing a diamine component having an aromatic ring or an alicyclic structure (that is, an aromatic diamine or an alicyclic diamine). .

The tetracarboxylic acid component given to the repeating unit of the aforementioned chemical formula (1-2) is a tetracarboxylic acid component given to the structure of the aforementioned chemical formula (A-3), and a tetracarboxylic acid component given to the structure of the aforementioned chemical formula (A-4) . Give the tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-3), for example: 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4,12: 6,10-di Methylanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, 3a, 4,6,6a, 9a, 10,12,12a-octahydro -1H, 3H-4,12-ethyl bridge-6,10-methanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4,12: 6,10-diethylanthracene [2,3-c: 6,7-c '] difuran -1,3,7,9-tetraone, 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4,12-ethylene bridge-6,10-methanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H -4,12: 6,10-diethylene bridge anthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone, and the corresponding tetracarboxylic acid, tetra A tetracarboxylic acid derivative other than a carboxylic dianhydride is given a tetracarboxylic acid component of the structure of the aforementioned chemical formula (A-4), for example: decahydro-1H, 3H-4,10-ethyl bridge-5,9-form Bridgenaphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone, and corresponding tetracarboxylic acids, and tetracarboxylic acids other than tetracarboxylic dianhydride derivatives Things. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used individually by 1 type, and may be used in combination of multiple types. Here, tetracarboxylic acids and the like refer to tetracarboxylic acid derivatives such as tetracarboxylic acid, tetracarboxylic dianhydride, silicon tetracarboxylic acid ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.

B ₁₂ in the aforementioned chemical formula (1-2) is a divalent group having an aromatic ring or an alicyclic structure. Considering the heat resistance of the obtained polyimide, the divalent group having an aromatic ring is preferably good. The B ₁₂ in the chemical formula (1-2), that is, the diamine component is not particularly limited, and may be appropriately selected according to the required characteristics and applications.

The diamine component of the repeating unit of the aforementioned chemical formula (1-2) is given, for example, the diamine component of the structure of the aforementioned chemical formula (B-1) given to the aforementioned polyfluorene imine precursor (1-1) and the aforementioned chemical formula ( Examples of the diamine component of the structure of B-2), and further, the diamine component of the structure of the aforementioned chemical formula (B-1) and the diamine component of the structure of the aforementioned chemical formula (B-2) Any of the diamine components of other repeating units can be used as desired. In the polyfluorene imide precursor (1-2), these diamine components may be used singly or in combination.

It is preferable that B ₁₂ in the aforementioned chemical formula (1-2) is a divalent group having an aromatic ring having 6 to 40 carbon atoms. The aforementioned chemical formula (B-1) exemplified by the aforementioned polyfluorene imine precursor (1-1) ) Is more ideal. The group represented by the aforementioned chemical formula (B-2) exemplified by the aforementioned polyfluorene imine precursor (1-1) is also preferable. B ₁₂ in the aforementioned chemical formula (1-2) is preferably a base represented by any one of the aforementioned chemical formulas (B-1-1) to (B-1-6) and (B-2-1).

B ₁₂ in the aforementioned chemical formula (1-2) is preferably a divalent group having a plurality of aromatic rings and one or all of the aromatic rings are connected by an ether bond (-O-). The following chemical formulas (B-3-1) ~ ( The base represented by any of B-3-4) is particularly desirable.

[Chemical 44]

In addition, B ₁₂ is a diamine component of the repeating unit of the aforementioned chemical formula (1-2) represented by the aforementioned chemical formula (B-3-1), and is 4,4'-oxydiphenylamine, and B ₁₂ is the aforementioned chemical formula. (B-3-2) The diamine component of the repeating unit of the aforementioned chemical formula (1-2) is 1,4-bis (4-aminophenoxy) benzene, and B ₁₂ is the aforementioned chemical formula (B -3-3) The diamine component of the repeating unit of the aforementioned chemical formula (1-2) is 1,3-bis (4-aminophenoxy) benzene, and B ₁₂ is given by the aforementioned chemical formula (B-3 -4) The diamine component of the repeating unit of the aforementioned chemical formula (1-2) is 4,4'-bis (4-aminophenoxy) biphenyl.

As described above, B ₁₂ in the chemical formula (1-2), that is, a diamine component, can be appropriately selected according to the required characteristics and applications. In an embodiment, in B ₁₂ in the aforementioned chemical formula (1-2), the base represented by the aforementioned chemical formula (B-1) and / or the base represented by the aforementioned chemical formula (B-2) is more preferably the aforementioned chemical formula (B -1-1) ~ (B-1-6), (B-2-1) The proportion of the base is preferably, for example, 50 mol% or more, more preferably 60 mol% or more , More preferably 65 mol% or more, more preferably 70 mol% or more, or more preferably 75 mol% or more. In an embodiment, in B ₁₂ in the aforementioned chemical formula (1-2), the divalent group having a plurality of aromatic rings and one or all of the aromatic rings are connected by an ether bond (-O-), and more preferably the aforementioned chemical formula The ratio of the bases represented by any of (B-3-1) to (B-3-4) is, for example, 30 mol% or more, and more preferably 50 mol% or more. In an embodiment, the proportion of the base represented by the aforementioned chemical formula (B-1) and / or the base represented by the aforementioned chemical formula (B-2) in B ₁₂ in the aforementioned chemical formula (1-2) is 60 mol in total. % Or more, preferably 65 mol% or more, or 70 mol% or more, or 75 mol% or more, the base represented by any one of the aforementioned chemical formulas (B-3-1) to (B-3-4) The proportion is 40 mol% or less in total, preferably 35 mol% or less, or 30 mol% or less, or 25 mol% or less.

The polyfluorene imide precursor (1-2) of the present invention may contain a repeating unit other than the repeating unit represented by the aforementioned chemical formula (1-2).

Other aromatic or aliphatic tetracarboxylic acids may be used as the tetracarboxylic acid component to give other repeating units. For example, the tetracarboxylic acid components given to other repeating units in the aforementioned polyfluorene imine precursor (1-1) may be listed and listed. For the same. In addition, a tetracarboxylic acid component given to the repeating unit of the aforementioned chemical formula (1-1) (that is, a tetracarboxylic acid component given to the structure of the aforementioned chemical formula (A-1), and a given formula (A-2) can be used. Structure of the tetracarboxylic acid component). In the polyfluorene imide precursor (1-2), the tetracarboxylic acid component given to these other repeating units may be used singly or in combination.

When the combined diamine component is a diamine having no aromatic ring and alicyclic structure, as for the tetracarboxylic acid component imparting other repeating units, a tetracarboxylic acid having a structure of the aforementioned chemical formula (A-3) can be used. One or two or more of the components and the tetracarboxylic acid component giving the structure of the aforementioned chemical formula (A-4).

As for the diamine component giving other repeating units, other aromatic or aliphatic diamines can be used, for example, and the diamine component giving other repeating units in the aforementioned polyfluorene imine precursor (1-1) is listed Those are the same. Further, a diamine component given to the repeating unit of the aforementioned chemical formula (1-1) (that is, a diamine component given to the structure of the aforementioned chemical formula (B-1), and a structure given to the aforementioned chemical formula (B-2) can be used. Of the diamine component). In the polyfluorene imide precursor (1-2), the diamine component to which these other repeating units are given may be used alone or in combination.

In the polyimide precursor [polyimide precursor (1-1), polyimide precursor (1-2)] of the present invention, X ₁ and X ₂ in the aforementioned chemical formula (1-1) _and in the aforementioned chemical formula (1-2) X _3, X ₄ are each independently hydrogen, 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, the carbon atoms or alkyl of 3 to 9 silicon Any one of the bases. X ₁ , X ₂ , X ₃ , and X ₄ can be changed in the type of functional group and the introduction rate of functional group according to the production method described later.

When X ₁ and X ₂ , X ₃ and X ₄ are hydrogen, the production of polyimide tends to be easy.

When X ₁ and X ₂ , X ₃ and X ₄ are alkyl groups having 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms, the storage stability of the polyfluorene imide precursor tends to be excellent. In this case, X ₁ and X ₂ , X ₃ and X _{4 are more} preferably methyl or ethyl.

When X ₁ and X ₂ , X ₃ and X ₄ are alkylsilyl groups having 3 to 9 carbon atoms, the solubility of the fluorene imine precursor tends to be excellent. In this case. X ₁ and X ₂ , X ₃ and X _{4 are more} preferably a trimethylsilyl group or a third butyldimethylsilyl group.

The introduction rate of the functional group is not particularly limited. When an alkyl group or an alkylsilyl group is introduced, X ₁ and X ₂ , X ₃ and X _{4 may} each be 25% or more, preferably 50% or more, and more preferably 75% or more. Alkyl or alkylsilyl.

Polyimide precursor of the present invention, by X ₁ and X _2, X ₃ and X ₄ TAKEN chemical structure, can be classified into: 1) Polyamide acid (X ₁ and X _2, X ₃ and X ₄ Is hydrogen), 2) polyamidate (at least a part of X ₁ and X ₂ is an alkyl group, at least a part of X ₃ and X ₄ is an alkyl group), 3) 4) polysilicic acid silicon ester (X ₁ And at least a part of X ₂ is an alkylsilyl group, and at least a part of X ₃ and X ₄ is an alkylsilyl group). In addition, the polyimide precursor of the present invention can be easily produced by the following production methods for its classification. However, the manufacturing method of the polyimide precursor of this invention is not limited to the following manufacturing methods.

1) Polyfluorinated acid The polyfluorinated imide precursor of the present invention can be obtained by using the tetracarboxylic dianhydride as the tetracarboxylic acid component and the diamine component in the solvent to approximately equal mole, preferably the diamine component is opposite. The molar ratio of the tetracarboxylic acid component [mole number of the diamine component / mole number of the tetracarboxylic acid component] is preferably 0.90 to 1.10, and more preferably 0.95 to 1.05, for example, a comparison below 120 ° C It can be obtained as a composition of a polyfluorene imine precursor solution while suppressing the reaction of fluorene imidization at a low temperature.

The method for synthesizing the polyfluorene imide precursor of the present invention is not limited, but more specifically, by dissolving the diamine in an organic solvent, slowly adding tetracarboxylic dianhydride to this solution while stirring, at 0 to 120 Stir for 1 to 72 hours at a temperature in the range of preferably 5 to 80 ° C to obtain a polyimide precursor. When the reaction is carried out at 80 ° C or higher, the molecular weight varies depending on the temperature history during the polymerization and the fluorene imidization is performed due to heat. Therefore, the polyfluorene imide precursor may not be produced stably. In the above manufacturing method, the order of addition of the diamine and the tetracarboxylic dianhydride is likely to increase the molecular weight of the polyfluorene imide precursor, so it is preferable. In addition, the order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method may be reversed, and it is preferable to consider the viewpoint of reducing precipitates.

In addition, when the molar ratio of the tetracarboxylic acid component and the diamine component is excessive by the diamine component, a carboxylic acid derivative having a molar amount approximately equal to the excess molar number of the diamine component may be added as needed to make the tetracarboxylic acid component and the diamine component The molar ratio of the amine component is approximately equivalent. Here, the carboxylic acid derivative is preferably a tetracarboxylic acid that does not substantially increase the viscosity of the polyfluorene imide precursor solution, that is, a tetracarboxylic acid that does not substantially involve the extension of the molecular chain, or a tricarboxylic acid that acts as a terminal stopper and Its anhydride, dicarboxylic acid and its anhydride.

2) Polyamic acid ester is obtained by reacting a tetracarboxylic dianhydride with an arbitrary alcohol to obtain a diester dicarboxylic acid, and then reacting it with a chlorinated reagent (such as thionyl chloride, chloracetin, etc.) to obtain a diester Dicarboxylic acid chloride. By stirring the diester dicarboxyphosphonium chloride and diamine at -20 to 120 ° C, preferably -5 to 80 ° C, for 1 to 72 hours, a polyfluorene imide precursor can be obtained. When the reaction is carried out at a temperature above 80 ° C, the molecular weight varies depending on the temperature history during the polymerization, and the fluorene imidization is performed due to heat. Therefore, the polyfluorene imide precursor may not be produced stably. Moreover, a polyimide precursor can also be obtained simply by carrying out dehydration condensation of a diester dicarboxylic acid and a diamine using a phosphorus-type condensation agent, a carbodiimide condensation agent, etc.

Because the polyimide precursor obtained in this way is stable, solvents such as water and alcohol can be added and refined by reprecipitation.

3) Polysiloxane (indirect method) The diamine is reacted with a silylating agent in advance to obtain a silylated diamine. If necessary, purification of silylated diamine is performed by distillation or the like. And in a dehydrated solvent, first dissolve the silylated diamine, and slowly add tetracarboxylic dianhydride while stirring. Stir for 1 to 72 hours at 0 to 120 ° C, preferably 5 to 80 ° C. To obtain a polyimide precursor. When the reaction is performed at a temperature of 80 ° C or higher, the molecular weight varies depending on the temperature history during polymerization, and the fluorene imidization progresses due to heat. Therefore, the polyfluorene imide precursor may not be produced stably.

If the silylating agent used here does not contain a chlorine-based silylating agent, it is not necessary to refine the silylated diamine, so it is ideal. Examples of the silylating agent not containing chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, and hexamethyldisilazide. Nitrogen. From the viewpoint of not containing a fluorine atom and being a low cost, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable.

In the silylation reaction of diamines, in order to promote the reaction, amine catalysts such as pyridine, piperidine, and triethylamine can be used. This catalyst can be used directly as a polymerization catalyst for polyimide precursors.

4) Polysiloxane (direct method) The polyamino acid solution obtained in the method of 1) is mixed with a silylating agent, and stirred at a temperature of 0 ~ 120 ° C, preferably 5 ~ 80 ° C, for 1 ~ 72 hours to obtain a polyimide precursor. When the reaction is carried out at a temperature of 80 ° C or higher, the molecular weight changes depending on the temperature history during polymerization, and the fluorene imidization progresses due to heat. Therefore, the polyfluorene imide precursor may not be produced stably.

If the silylating agent used here is a silylating agent that does not contain chlorine, it is not necessary to refine the silylated polyamic acid or the obtained polyimide, which is ideal. Examples of the silylating agent not containing chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, and hexamethyldisilazide. Nitrogen. Considering the viewpoint of containing no fluorine atom and low cost, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable.

The aforementioned manufacturing methods can all be performed ideally in an organic solvent, and as a result, the varnish of the polyimide precursor of the present invention can be easily obtained.

Solvents used in the preparation of polyimide precursors, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl Aprotic solvents such as methyl-2-imidazolidinone and dimethylsulfinyl are preferred, especially N, N-dimethylacetamidamine and N-methyl-2-pyrrolidone are preferred, but as long as the raw material monomer The components and the produced polyimide precursor will dissolve, and any kind of solvent can be used without any problem, so its structure is not particularly limited. As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amine solvents, γ-butyrolactone, γ-valerolactone, δ-pentyl Cyclic ester solvents such as lactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, triethylene glycol, etc. Diol solvents, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidone, cyclobutane Methyl fluorene is preferred. Furthermore, other general organic solvents can also be used, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyperidine, butyl cyperone Threon, 2-methylcythrethacetate, ethylcythrethacetate, butylcythrethacetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether , Diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits , Petroleum brain solvent. A plurality of solvents may be used in combination.

In the present invention, the logarithmic viscosity of the polyfluorene imide precursor is not particularly limited, and the logarithmic viscosity in a N, N-dimethylacetamide solution at a concentration of 30 g at 0.5 g / dL is 0.2 dL / g or more, It is preferably 0.3 dL / g or more. If the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide has excellent mechanical strength and heat resistance.

In the present invention, the polyimide precursor varnish contains at least the polyimide precursor of the present invention [polyimide precursor (1-1) and / or polyimide precursor (1-2)] With solvent. Relative to the total amount of the solvent, the tetracarboxylic acid component and the diamine component, the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. . The total amount of the tetracarboxylic acid component and the diamine component is usually 60% by mass or less, and preferably 50% by mass or less based on the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. This concentration is approximately similar to the concentration of the solid component concentration of the polyimide precursor. If the concentration is too low, for example, it is difficult to control the film thickness of the polyimide film obtained when manufacturing the polyimide film.

The solvent used in the varnish of the polyimide precursor of the present invention is not a problem as long as the polyimide precursor is soluble, and its structure is not particularly limited. Examples of the solvent include amine solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, Cyclic ester solvents such as δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethyl carbonate and propylene carbonate, triethyl Diol solvents such as diols, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane Rhenium, dimethyl sulfene and the like are preferred. In addition, other general organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyperidine, butyl cyperidine, 2 -Methyl cyperidine acetate, ethyl cyperidine acetate, butyl cyperidine acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethyl Dimethyl glycol ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits, petroleum brain A solvent or the like can also be used. Moreover, most of them can be used in combination. In addition, as the solvent of the varnish of the polyfluorene imide precursor, a solvent used in preparing the polyfluorene imide precursor can be directly used.

In the present invention, the viscosity (rotary viscosity) of the varnish of the polyimide precursor is not particularly limited. The rotational viscosity measured by using an E-type rotary viscometer at a temperature of 25 ° C and a shear rate of 20 sec ^-1 is 0.01 to 1000 Pa · sec More ideal, 0.1 ~ 100Pa ・ sec is more ideal. If necessary, thixotropy may be imparted. When the viscosity is within the above range, it is easy to handle and suppress eye holes during coating and film formation, and it is excellent in flatness and good film.

According to the varnish of the polyfluorene imide precursor of the present invention, chemical fluorimide (anhydride compounds such as acetic anhydride, amine compounds such as pyridine, isoquinoline), antioxidants, and fillers (inorganic particles such as silicon dioxide) may be added as needed. Etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), release agents, etc.

The polyimide (hereinafter also referred to as "polyimide (2-1)") of the first aspect of the present invention contains at least one of the repeating units represented by the aforementioned chemical formula (2-1), and The total content of the repeating units represented by this chemical formula (2-1) is 50 mol% or more of polyimide with respect to the total repeating units. That is, the polyfluorene imine (2-1) of the present invention can be obtained by using the aforementioned tetracarboxylic acid component and diamine component used in order to obtain the polyfluorine imine precursor (1-1) of the present invention. The carboxylic acid component and the diamine component are also the same as the polyfluorene imine precursor (1-1) of the present invention.

The aforementioned chemical formula (2-1) corresponds to the aforementioned chemical formula (1-1) of the polyfluorene imine precursor (1-1), and each of A ₂₁ and B ₂₁ in the aforementioned chemical formula (2-1) corresponds to the aforementioned chemical formula. A ₁₁ and B ₁₁ in (1-1).

The polyimide (hereinafter also referred to as "polyimide (2-2)") of the second aspect of the present invention is a polyimide containing at least one of the repeating units represented by the aforementioned chemical formula (2-2).醯 imine. The total content of the repeating units represented by the chemical formula (2-2) is not particularly limited, and it is preferably 50 mol% or more relative to the total repeating units. That is, the polyfluorene imine (2-2) of the present invention can be obtained by using the aforementioned tetracarboxylic acid component and diamine component used in order to obtain the polyfluorene imine precursor (1-2) of the present invention. The tetracarboxylic acid component and the diamine component are also the same as the polyfluorene imide precursor (1-2) of the present invention.

The aforementioned chemical formula (2-2) corresponds to the aforementioned chemical formula (1-2) of the polyimide precursor (1-2), and A ₂₂ and B ₂₂ in the aforementioned chemical formula (2-2) respectively correspond to the aforementioned chemical formula. A ₁₂ and B ₁₂ in (1-2).

The polyfluorene imine (2-1) of the present invention can be ideally produced by subjecting the polyfluorene imine precursor (1-1) of the present invention as described above to a dehydration ring-closing reaction (fluorene imidization reaction). The polyfluorene imine (2-2) of the present invention can be ideally produced by subjecting the polyfluorene imine precursor (1-2) of the present invention as described above to a dehydration ring-closing reaction (fluorene imidization reaction). The method of fluorene imidization is not particularly limited, and a known method of thermal fluoridation or chemical fluoridation can be preferably used.

As the form of the obtained polyimide, a film, a laminate of a polyimide film and another substrate, a coating film, a powder, beads, a molded body, a foam, and a varnish can be suitably cited.

In the present invention, the logarithmic viscosity of polyfluoreneimine is not particularly limited, and the logarithmic viscosity in a N, N-dimethylacetamide solution at a concentration of 30 g at 0.5 g / dL is 0.2 dL / g or more, more preferably 0.4 dL / g or more, particularly preferably 0.5 dL / g or more. If the logarithmic viscosity is 0.2 dL / g or more, the obtained polyimide has excellent mechanical strength and heat resistance.

In the present invention, the polyimide varnish contains at least the polyimide and the solvent of the present invention, and the polyimide is 5% by mass or more, preferably 10% by mass, relative to the total amount of the solvent and the polyimide. Above, more preferably 15% by mass or more, particularly preferably 20% by mass or more. If the concentration is too low, for example, it may be difficult to control the film thickness of the obtained polyimide film when manufacturing the polyimide film.

If the solvent used for the polyimide varnish of the present invention is soluble, there is no problem and the structure is not particularly limited. The solvent may be the same as that used for the varnish of the polyimide precursor of the present invention.

In the present invention, the viscosity (rotary viscosity) of the polyimide varnish is not particularly limited. It is preferable that the rotational viscosity measured by using an E-type rotary viscometer at a temperature of 25 ° C. and a shear rate of 20 sec ^-1 is 0.01 to 1000 Pa · sec. , 0.1 ~ 100Pa · sec is more ideal. If necessary, thixotropy may be imparted. The viscosity in the above range is easy to handle during coating and film formation. In addition, eye holes are suppressed, the flatness is excellent, and a good film can be obtained.

In the polyimide varnish of the present invention, coupling agents such as antioxidants, fillers (inorganic particles such as silicon dioxide, etc.), dyes, pigments, silane coupling agents, primers, and flame-retardant materials may be added as needed. , Antifoaming agent, leveling agent, rheological air preparation (flow aid), release agent, etc.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the linear thermal expansion coefficient at 100 ° C to 250 ° C when the film is made is preferably 45 ppm / K or less, more preferably It is 40 ppm / K or less. If the coefficient of linear thermal expansion is large, the difference between the coefficient of linear thermal expansion and a conductor such as a metal is large, and there may be disadvantages such as increased warpage when forming a circuit board.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the total light transmittance (average light transmittance at a wavelength of 380 to 780 nm) of a film having a thickness of 10 μm is preferably Above 70%, more preferably above 75%, and even more preferably above 80%. When used in display applications, etc., if the total light transmittance is low, the light source needs to be strengthened, which may cause problems such as energy consumption.

In addition, depending on the application, the film made of the polyfluorene imide of the present invention has a thickness of preferably 1 μm to 250 μm, more preferably 1 μm to 150 μm, still more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the polyimide film is used in a light-transmitting application such as a display application, if the polyimide film is too thick, there is a possibility that the light transmittance may decrease.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the 5% weight reduction temperature which is an index of the heat resistance of the polyimide is preferably 420 ° C or more, more Preferably it is above 450 ° C. When a transistor is formed on polyimide, a gas barrier film is formed on the polyimide, etc., if the heat resistance is low, the polyimide may be decomposed by the polyimide, etc. The accompanying fugitive gas causes the uplift to occur.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be applied to, for example, a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell.

An example of a method for producing a polyimide film / substrate laminate or a polyimide film using the polyimide precursor of the present invention is described below. It is not limited to the following methods.

The varnish of the polyimide precursor of the present invention is cast on a base such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat-resistant plastic film (polyimide film, etc.), etc. The material is dried in a vacuum in an inert gas such as nitrogen or hot air or infrared in the air at a temperature range of 20 to 180 ° C, preferably 20 to 150 ° C. Secondly, the obtained polyimide precursor film can be detached from the substrate, or the polyimide precursor film can be peeled from the substrate, and the end of the film can be fixed. In a vacuum, nitrogen or the like is blunt. In hot gas or air, use hot air or infrared rays, for example, at 200 to 500 ° C, more preferably 250 to 460 ° C, to heat and imidize to produce a polyimide film / substrate laminate. , Or polyimide film. In addition, in order to prevent the oxidative degradation of the obtained polyfluorene imide film, it is preferable to perform the heating fluorimide in a vacuum or in an inert gas. If the temperature of the imidization by heating is not too high, it may be carried out in the air.

In addition, the fluorene imidization reaction of the polyfluorene imine precursor can also be replaced by the presence of the polyfluorene imine precursor in a tertiary amine such as pyridine, triethylamine, etc. Chemical treatment such as immersion in a solution containing a dehydration cyclization reagent such as acetic anhydride is performed. In addition, the dehydration cyclization reagents are put into a polyimide precursor varnish and stirred in advance, and the casted substance is cast on a substrate and dried to obtain a partially fluorinated polyimide. Amine precursor, a state in which the obtained partially imidized polyfluorene imide precursor film is on a substrate, or a polyimide precursor film is peeled from a substrate, and is fixed at the end of the film Further, if the heat treatment is performed as described above, a polyimide film / substrate laminate or a polyimide film can be obtained.

By forming a polyimide film / base material laminate or a polyimide film obtained in this manner, a flexible conductive substrate can be obtained by forming a conductive layer on one or both sides.

A flexible conductive substrate can be obtained by the following method, for example. That is, in the first method, instead of peeling the polyimide film / substrate laminate from the base material, the polyimide film surface is sputtered, vapor-deposited, and printed. The conductive layer (such as metal or metal oxide, conductive organic substance, conductive carbon, etc.) is formed to form a conductive laminate of a conductive layer / polyimide film / base material. Thereafter, if necessary, the conductive layer / polyimide film laminate is peeled from the substrate, thereby obtaining a transparent and flexible conductive substrate composed of the conductive layer / polyimide film laminate. .

In the second method, the polyimide film can be peeled off from the base material of the polyimide film / substrate laminate to obtain a polyimide film. The surface of the polyimide film is the same as the first method. Form a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, etc.) to obtain a conductive layer / polyimide film laminate, or a conductive layer / polyimide film / A transparent and flexible conductive substrate made of a conductive laminate.

In the first and second methods, if necessary, a gas barrier layer such as water vapor or oxygen may be formed by sputtering, vapor deposition, gel-sol method, or the like before forming a conductive layer on the surface of the polyimide film. , Light adjustment layer and other inorganic layers.

The conductive layer can be formed into a circuit by a method such as photolithography, various printing methods, and inkjet methods.

In the substrate of the present invention obtained in this manner, a circuit having a conductive layer formed between the gas barrier layer and the inorganic layer on the surface of the polyimide film composed of the polyimide of the present invention as required. This substrate is flexible and easily forms fine circuits. Therefore, this substrate is suitable as a substrate for a display, a touch panel, or a solar cell.

That is, the substrate is further formed with a transistor (inorganic transistor, organic transistor) by vapor deposition, various printing methods, or inkjet methods, and a flexible thin-film transistor is manufactured. The substrate is suitable for use as a liquid crystal element for display and EL Element, optoelectronic element.

The tetracarboxylic dianhydride used in the production of the polyfluorene imide precursor (1-2) of the present invention and the polyfluorene imine (2-2) of the present invention is the tetracarboxylic acid dianhydride represented by the aforementioned chemical formula (M-1) The anhydride and the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) are novel compounds.

Hereinafter, the manufacturing method of the tetracarboxylic dianhydride represented by the said chemical formula (M-1) is described.

For the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-1), refer to Japanese Patent Application Laid-Open No. 2010-184898, J. Chin. Chem. Soc. 1998, 45, 799, Tetrahedron 1998, 54, 7013, Helvetica. Chim Acta. 2003, 86, 439, Angew. Chem. Int. Ed. Engl. 1989, 28, 1037, etc. were synthesized according to the reaction scheme shown below, for example. Here, it is a tetracarboxylic dianhydride represented by the chemical formula (M-1) in which R ₅ ′ and R ₆ ′ are —CH ₂ —, that is, 3a, 4, 6, 6a, 9a, 10, 12, 12a- Octahydro-1H, 3H-4,12: 6,10-dimethyl bridge anthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone (DMADA) As an example, other tetracarboxylic dianhydrides can be produced similarly.

式中，R為也可以有取代基之烷基或芳基，R₁₁ 、R₁₂ 、R₁₃ 、R₁₄ 各自獨立地為碳數1~10之烷基。[Chemical 45]

In the formula, R is an alkyl group or an aryl group which may have a substituent, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.

(Step 1) In the first step, when the tetracarboxylic dianhydride (DMADA) of the chemical formula (M-1) of R ₅ ′ and R ₆ ′ -CH ₂ -is synthesized, p-benzoquinone (BQ) and Cyclopentadiene (CP) reaction to synthesize 1,4,4a, 5,8,8a, 9a, 10a-octahydro-1,4: 5,8-dimethylmethanthracene-9,10-dione (DNBQ ). When synthesizing a tetracarboxylic dianhydride of the formula (M-1) in which R ₅ ′ and R ₆ ′ are —CH ₂ CH ₂ —, cyclopentadiene (CP) is replaced by 1,3-cyclohexadiene. The olefin can be reacted with BQ.

The amount of the aforementioned cyclopentadiene (or 1,3-cyclohexadiene, etc.) is preferably 1.0 to 20 mol, and more preferably 1.5 to 10.0 mol relative to 1 mol of p-benzoquinone (BQ). .

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等鹵化烴類；乙酸乙酯、乙酸丁基等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為醇類、芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and other amines; N, N -Ureas such as dimethyl imidazolidone; fluorenes such as dimethyl fluorene and cyclobutane; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; diisopropyl ether, di

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; methylene chloride, chloroform, 1 , 2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably alcohols, aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and is preferably 1 to 50 g, and more preferably 2 to 30 g, relative to BQ1 g.

This reaction can be carried out by, for example, a method of mixing and stirring BQ and CP in an organic solvent. The reaction temperature at this time is preferably 0 to 150 ° C, and more preferably 15 to 60 ° C. The reaction pressure is not particularly limited.

(Second step) The second step is to react the DNBQ obtained in the first step with sodium borohydride to synthesize 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydro-1,4 : 5,8-dimethyl bridge anthracene-9,10-diol (DNHQ).

The use amount of the aforementioned sodium borohydride is preferably 0.5 to 10 mol, and more preferably 1.5 to 5.0 mol relative to DNBQ1 mol.

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；乙酸乙酯、乙酸丁基等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為醇類、醚類、芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and other amines; N, N -Ureas such as dimethyl imidazolidone; fluorenes such as dimethyl fluorene and cyclobutane; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; diisopropyl ether, di

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; ethyl acetate, butyl acetate And other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably alcohols, ethers, and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted according to the uniformity and agitation of the reaction liquid, but it is preferably 1 to 100 g, and more preferably 5 to 50 g, relative to DNBQ1 g.

This reaction can be performed by, for example, mixing and stirring DNBQ with sodium borohydride in an organic solvent. The reaction temperature at this time is preferably -20 to 150 ° C, and more preferably 0 to 50 ° C. The reaction pressure is not particularly limited.

(3rd step) The third step is to react the DNHQ obtained in the second step with methanesulfonyl chloride in the presence of a base to synthesize dimethylsulfonic acid 1,4,4a, 5,8,8a, 9,9a, 10 , 10a-decahydro-1,4: 5,8-dimethyl bridge anthracene-9,10-diester (DNCMS; in this case R is -CH ₃ [-SO ₂ R is methanesulfonyl (-SO ₂ CH ₃ )]). Methanesulfonyl chloride can also be replaced with other aliphatic sulfonyl chloride or aromatic sulfonyl chloride.

This reaction uses a base. The bases used in this reaction are, for example, secondary amines such as dibutylamine, piperidine, and 2-methylpiperidine; tertiary amines such as triethylamine, tributylamine; pyridine, methylpyridine, and dimethylamine Pyridines such as pyridine; quinolines such as quinoline, isoquinoline, and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, etc. Alkali metal alkoxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, preferably tertiary amines Type, pyridine type, quinoline type, alkali metal carbonate. These bases can be used alone or in combination of two or more.

The amount of the aforementioned base to be used is preferably 0.01 to 200 moles, more preferably 0.1 to 100 moles relative to DNHQ1 mole.

This reaction uses sulfonium chloride. Sulfasulfonium chloride used in this reaction, for example: aliphatic sulfonium chloride such as methanesulfonyl chloride, ethanesulfonyl chloride, trifluoromethanesulfonyl chloride; benzenesulfonyl chloride, tosylsulfonium chloride, nitrobenzenesulfonyl chloride Aromatic sulfonyl chloride, such as chlorine, is preferably an aliphatic sulfonyl chloride. In addition, these sulfonyl chlorides can be used alone or in combination of two or more.

The amount of sulfonyl chloride used is preferably 1.5 to 10 moles, and more preferably 1.8 to 5 moles, relative to DNHQ1 mole.

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；乙酸乙酯、乙酸丁基等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為吡啶類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and other amines; N, N -Ureas such as dimethylimidazolidone; pyridines such as pyridine, methylpyridine, dimethylaminopyridine; quinolines such as quinoline, isoquinoline, methylquinoline; dimethylsulfinium, cyclobutane Rhenium and other fluorenes; acetonitrile, propionitrile and other nitriles; diisopropyl ether, two

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; ethyl acetate, butyl acetate And other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably pyridines. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 1 to 200 g, and more preferably 10 to 100 g, relative to 1 g of DNHQ.

This reaction can be performed, for example, by mixing and stirring DNHQ, alkali, and sulfonium chloride in an organic solvent. The reaction temperature at this time is preferably -20 to 150 ° C, and more preferably 0 to 50 ° C. The reaction pressure is not particularly limited.

(Fourth step) In the fourth step, methanol was reacted with carbon monoxide and the DNCMS obtained in the third step in the presence of a palladium catalyst and a copper compound to synthesize 9,10-bis ((methylsulfonyl) oxy) 14 Hydrogen-1,4: 5,8-dimethyl bridge anthracene-2,3,6,7-tetracarboxylic acid tetramethyl ester (DNMTE; in this case R ₁₁ to R ₁₄ are methyl). Alternatively, methanol may be replaced with another alcohol compound corresponding to the desired ester compound.

Alcohol compounds used in this reaction, such as: methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol, and the like are preferably methanol, ethanol, n-propanol, and isopropanol, and more preferably methanol, ethanol, and isopropanol. These alcohol compounds may be used alone or in combination of two or more.

The amount of the alcohol compound is preferably 1 to 100 g, and more preferably 5 to 50 g, relative to 1 g of DNCMS.

This reaction uses a palladium catalyst. The palladium catalyst used in the reaction is not particularly limited as long as it contains palladium, for example: palladium halide such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and oxalate; palladium inorganic acid salts such as palladium nitrate and palladium sulfate ; Palladium carbon, palladium alumina, and the like supported by palladium supported on carbon, alumina, and the like, preferably palladium chloride and palladium carbon.

The use amount of the aforementioned palladium catalyst is preferably 0.001 to 1 mol, and more preferably 0.01 to 0.5 mol relative to DNCMS1 mol.

This reaction uses a copper compound. Copper compounds used in this reaction, such as: copper (I) oxide, copper (I) chloride, copper (I) bromide and other equivalent copper compounds, copper (II) oxide, copper (II) chloride, bromide A divalent copper compound such as copper (II), etc., is preferably a divalent copper compound, and more preferably copper (II) chloride. Moreover, these copper compounds can be used individually or in mixture of 2 or more types.

The use amount of the aforementioned copper compound is preferably 1.0 to 50 mol, and more preferably 4.0 to 20 mol relative to DNCMS1 mol.

烷、1,2-亞甲基二氧苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為脂肪族烴類、芳香族烴類、鹵化烴類、鹵化芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。In this reaction, an organic solvent other than the aforementioned alcohol compound may be used. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: aliphatic carboxylic acids (for example, formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example, methanesulfonic acid, trifluoromethanesulfonic acid) Etc.), ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), ammonium (for example: N , N-dimethylformamidine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. : Diethyl ether, diisopropyl ether, tetrahydrofuran, di

Alkanes, 1,2-methylene dioxobenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 1 to 100 g, and more preferably 5 to 50 g, relative to 1 g of DNCMS.

This reaction can be performed, for example, by mixing DNCMS, an alcohol compound, a palladium catalyst, and a copper compound in a organic solvent, and stirring under a carbon monoxide gas environment. The reaction temperature at this time is preferably -20 to 100 ° C, and more preferably 0 to 50 ° C. The reaction pressure is not particularly limited.

(Fifth step) In the fifth step, 1,2,3,4,4a, 5,6,7,8,9a-decahydro was synthesized by the demethane sulfonylation reaction of DNMTE obtained in the fourth step. -1,4: 5,8-dimethyl bridge anthracene-2,3,6,7-tetracarboxylic acid tetramethyl ester (DMHAE). The compound obtained in this step 5 is a tetraester compound represented by the aforementioned chemical formula (M-3) and is a novel compound.

This reaction can be carried out by, for example, using DNMTE in an organic solvent, and stirring while heating as necessary. The reaction temperature at this time is preferably -20 to 200 ° C, and more preferably 25 to 180 ° C. The reaction pressure is not particularly limited.

This reaction can be carried out by heating and stirring even without adding a base to the reaction solution, but in order to capture by-product strong acidic methanesulfonic acid, a base is preferably used. The base used is not particularly limited as long as it does not interfere with the reaction, for example: secondary amines such as dibutylamine, piperidine, 2-methylpiperidine; tertiary amines such as triethylamine, tributylamine; pyridine, methylpyridine , Pyridines such as dimethylaminopyridine; quinolines such as quinoline, isoquinoline, methylquinoline; alkali metal hydrides such as sodium hydride, potassium hydride; sodium methoxide, sodium ethoxide, sodium isopropoxide, third Alkali metal alkoxides such as potassium butoxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide , Preferably tertiary amines, pyridines, quinolines, alkali metal carbonates. These bases can be used alone or in combination of two or more.

The amount of the aforementioned base to be used is preferably 1.5 to 5 mol, and more preferably 1.8 to 3 mol, relative to 1 Dmol.

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等鹵化烴類；乙酸乙酯、乙酸丁酯等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為醯胺類、尿素類、腈類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethyl Imidamines such as isobutylphosphoniumamine; Ureas such as N, N-dimethylimidazolidone; Subfluorenes such as dimethylsulfinium and cyclobutyrium; nitriles such as acetonitrile and propionitrile; methanol, ethanol, Alcohols such as n-propanol, isopropanol, n-butanol, and tertiary butanol; diisopropyl ether, two

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; methylene chloride, chloroform, 1 , 2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably amines, ureas, nitriles. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and is preferably 1 to 100 g, and more preferably 2 to 50 g, relative to 1 g of DNMTE.

(Step 6) In step 6, 1,2,3,4,5,6,7,8-octahydro-1,4 is synthesized from the aromaticization reaction (oxidation reaction) of DMHAE obtained in step 5. : Tetramethyl 5,8-dimethyl bridge anthracene-2,3,6,7-tetracarboxylic acid (DMAME). The compound obtained in this step 6 is a tetraester compound represented by the aforementioned chemical formula (M-2), and is a novel compound.

This reaction can be performed, for example, by a method such as stirring DMHAE and an aromatic oxidizing agent in a solvent while heating as necessary. The reaction temperature at this time is preferably 25 to 150 ° C, and more preferably 40 to 120 ° C. The reaction pressure is not particularly limited.

In this reaction, an oxidizing agent is used for aromatization. The oxidizing agent used is not particularly limited as long as it does not interfere with the reaction, and for example, benzoquinones such as 2,3-dichloro-5,6-dicyano-p-benzoquinone and tetrachlorobenzoquinone can be used.

The amount of the aforementioned oxidizing agent is preferably 0.5 to 5 moles, and more preferably 0.8 to 3 moles relative to DMHAE1 mole.

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等鹵化烴類；乙酸乙酯、乙酸丁酯等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為芳香族烴類、鹵化烴類、醚類、醇類、水。又，該等溶劑可單獨使用或混用二種以上。This reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: water; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethyl Imidamines such as isobutylammonium amine; ureas such as N, N-dimethylimidazolidone; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; diisopropyl ether, di

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; methylene chloride, chloroform, 1 2,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably aromatic hydrocarbons, halogenated hydrocarbons, ethers Alcohol, alcohol, water. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, but it is preferably 1 to 100 g, and more preferably 2 to 50 g, relative to 1 g of DMHAE.

(Step 7) In the seventh step, 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4,12 are synthesized by the anhydrous reaction of DMAME obtained in the sixth step: 6,10-dimethylmethanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone (DMADA). The compound obtained in this seventh step is a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-1).

This reaction can be performed by a method such as stirring DMAME in an organic solvent in the presence of an acid catalyst while heating. The reaction temperature at this time is preferably 50 to 130 ° C, and more preferably 80 to 120 ° C. The reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, for example: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid and other inorganic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel, zeolites, acid alumina, etc., preferably inorganic acids, organic sulfonic acids, and more preferably organic sulfonic acids. These acids can be used alone or in combination of two or more.

The amount of the aforementioned acid catalyst is preferably 0.0001 to 0.1 mole, and more preferably 0.001 to 0.05 mole relative to DMAME1 mole.

This reaction is preferably carried out in a solvent. The solvent used is preferably an organic acid solvent such as formic acid, acetic acid, and propionic acid. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.1 to 100 g, and more preferably 1 to 10 g, relative to 1 g of DMAME.

The details of each reaction are explained according to the examples, but those with ordinary knowledge in the technical field can change the solvent, feed amount, reaction conditions, etc. After the completion of each reaction, for example, filtration, extraction, distillation, sublimation, Recrystallization, column chromatography and other general methods are used to isolate and purify the reaction product.

A method for producing the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) will be described below.

For the tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4), reference may be made to Helv. Chim. Acta. 1975, 58, 160, Macromolecules 1993, 26, 3490, and the like, for example, according to the reaction scheme shown below.

式中，X₁₁ 、X₁₂ 各自獨立地為-F、-Cl、-Br、或-I，R₂₁ 、R₂₂ 、R₂₃ 、R₂₄ 各自獨立地為碳數1~10之烷基。[Chemical 46]

In the formula, X ₁₁ and X ₁₂ are each independently -F, -Cl, -Br, or -I, and R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbon atoms.

(First step) In the first step, 5-norbornene-2,3-dicarboxylic anhydride (NA) is reacted with 1,3-butadiene to synthesize 3a, 4,4a, 5,8,8a, 9,9a-octahydro-4,9-methanonaphtho [2,3-c] furan-1,3-dione (OMNA). The compound obtained in this first step is a dicarboxylic anhydride represented by the aforementioned chemical formula (M-7) and is a novel compound.

This reaction can be carried out by, for example, charging NA into a pressure-resistant container such as an autoclave, introducing 1,3-butadiene, heating and stirring. The reaction temperature at this time is preferably 80 to 220 ° C, and more preferably 100 to 180 ° C. The reaction pressure is not particularly limited.

The use amount of the aforementioned 1,3-butadiene is preferably 0.5 to 5 mol, and more preferably 0.8 to 3 mol relative to NA1 mol.

烷、1,2-亞甲基二氧基苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚等)等。較佳為使用脂肪族烴類、及芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction may or may not use an organic solvent. The solvent to be used is not particularly limited as long as it does not interfere with the reaction, for example: ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane Alkanes, etc.), amidines (for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylisobutylamidine Etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, diamine

Alkanes, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1,2-dichlorobenzene, etc.) , 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (for example: nitrobenzene, etc.), halogenated hydrocarbons (for example: dichloromethane, chloroform, tetrachloride) Carbon, 1,2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), Phosphonium (for example: dimethyl fluorene and the like), fluorene (for example: cyclobutyl fluorene and the like), phenols (phenol, methylphenol, p-chlorophenol, etc.) and the like. It is preferable to use aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

When an organic solvent is used, the amount of the organic solvent used can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.1 to 100 g, and more preferably 1 to 50 g, relative to NA 1 g.

(Second step) In the second step, the OMNA obtained in the first step is reacted with bromine as a dihalogenating agent to synthesize 6,7-dibromodecahydro-4,9-methacylnaphtho [2,3-c ] Furan-1,3-dione (DBDNA; in this case X ₁₁ and X ₁₂ are -Br). The bromine may be replaced with another dihalogenating agent described later. The compound obtained in this second step is a dihalodicarboxylic anhydride represented by the aforementioned chemical formula (M-6) and is a novel compound.

This reaction can be performed by, for example, mixing and stirring OMNA and a dihalogenating agent in an organic solvent. The reaction temperature at this time is preferably -100 to 50 ° C, and more preferably -80 to 30 ° C. The reaction pressure is not particularly limited.

This reaction uses a dihalogenating agent such as bromine. The dihalogenating agent used in this reaction is not particularly limited as long as it can dihalide an olefin, and examples thereof include halogens such as fluorine, chlorine, bromine, and iodine, and pyridine salts, ammonium salts, tribromopyridine, and tribromobenzyltrimethyl. Tribromide salts such as ammonium chloride, halogen compounds such as chlorine fluoride, bromine chloride, iodine chloride, iodine bromide, and iodine tribromide, and their pyridine salts, ammonium salts, etc., are preferably halogens, particularly preferably bromine.

The amount of the aforementioned dihalogenating agent is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles, relative to OMNA1 mole.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚)等。較佳為脂肪族烴類、鹵化烴類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction is usually performed in an organic solvent. The solvent to be used is not particularly limited as long as it does not interfere with the reaction, for example: ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane Alkanes, etc.), amidines (for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylisobutylamidine Etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, diamine

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol), and the like. Preferred are aliphatic hydrocarbons and halogenated hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.1 to 100 g, and more preferably 1 to 50 g, relative to 1 g of OMNA.

(Step 3) In step 3, the DBDNA obtained in step 2 is reacted with maleic anhydride to synthesize 3a, 4,4a, 5,5a, 8a, 9,9a, 10,10a-decahydro-1H, 3H -4,10-Ethyl bridge-5,9-methyl bridgenaphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone (EEMDA). The compound obtained in this third step is a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) of the R ₇ series -CH = CH-, and is a novel compound.

This reaction can be performed by, for example, mixing DBDNA with maleic anhydride, heating and stirring. The reaction temperature at this time is preferably 100 to 250 ° C, and more preferably 120 to 230 ° C. The reaction pressure is not particularly limited.

The amount of the aforementioned maleic anhydride is usually 1 mol or more, preferably 2 mol or more, and more preferably 4 mol or more, relative to 1 DNA of the DNA molecule.

This reaction is performed by mixing solid DBDNA with maleic anhydride. The theoretically necessary amount of maleic anhydride with respect to DBDNA is 1 mol. However, when using about 1 mol, the reactant after the reaction may be solidified in the reaction container and difficult to remove. On the other hand, when maleic anhydride (melting point 52-56 ° C) is used in an amount exceeding isomolar, the reaction temperature is higher than the melting point of maleic anhydride, so excess maleic anhydride is a liquid, which acts as a solvent and reacts. The system becomes a suspension. After the reaction is completed, the reaction temperature is cooled to a temperature suitable for the operation (for example, about 100 ° C.), and an organic solvent is added to the system and filtered to obtain high-purity EEMDA.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為脂肪族烴類、及芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。Organic solvents added after the reaction, for example: ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), 醯Amines (for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylisobutylamidine, etc.), urea (N, N'-dimethylimidazolidone, etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, di

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), and the like. Preferred are aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the prepared solution, and is preferably 0.1 to 30 mL, and more preferably 0.5 to 20 mL, relative to 1 g of DBDNA.

(Step 4) In step 4, the EEMDA obtained in step 3 is reacted with methanol to synthesize 1,4,4a, 5,6,7,8,8a-octahydro-1,4-ethyl bridge-5. , 8-Methylnaphthalene-6,7,10,11-tetracarboxylic acid tetramethyl ester (EEMDE; in this case, R ₂₁ to R ₂₄ are methyl). Alternatively, methanol may be replaced with another alcohol compound corresponding to the desired ester compound. The compound obtained in this fourth step is a tetraester compound represented by the aforementioned chemical formula (M-5) in which R ₇ is -CH = CH-, and is a novel compound.

This reaction can be performed, for example, by mixing and stirring EEMDA, orthoesters, and alcohols in the presence of an acid. The reaction temperature at this time is preferably 20 to 150 ° C, and more preferably 50 to 100 ° C. The reaction pressure is not particularly limited.

This reaction uses an acid. There are no special restrictions on the acids used in this reaction, for example: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, and nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; chloroacetic acid Halogenated carboxylic acids, such as trifluoroacetic acid, ion exchange resins, silica gel, zeolites, acidic alumina, etc., are preferably inorganic acids, organic sulfonic acids, and more preferably inorganic acids. These acids can be used alone or in combination of two or more.

The amount of the aforementioned acid to be used is preferably 0.01 to 10 moles, more preferably 0.05 to 3 moles, relative to EEMDA1 mole.

This reaction uses an alcohol compound. Alcohol compounds used in this reaction, such as: methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol and the like are preferably methanol, ethanol, n-propanol, isopropanol, and more preferably methanol and ethanol. These alcohol compounds may be used alone or in combination of two or more.

The amount of the aforementioned alcohol compound is preferably 0.1 to 200 g, and more preferably 1 to 100 g, relative to EEMDA 1 g.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為脂肪族烴類、芳香族烴類、鹵化烴類、鹵化芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。In this reaction, organic solvents other than the aforementioned alcohols may be used. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: aliphatic carboxylic acids (for example: formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example: methanesulfonic acid, trifluoromethanesulfonic acid) Etc.), ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), ammonium (for example: N , N-dimethylformamidine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. : Diethyl ether, diisopropyl ether, tetrahydrofuran, di

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the organic solvent other than the aforementioned alcohols is preferably 0.1 to 200 g, and more preferably 1 to 100 g, relative to 1 g of EEMDA.

This reaction can use orthoesters. The orthoesters to be used include compounds represented by the following formulas, for example: trimethyl orthoformate and triethyl orthoformate, preferably trimethyl orthoformate.

[Chemical 47]

In the formula, R ^f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. And, R ^e is alkyl of 1 to 5, preferably methyl, ethyl, more preferably methyl. The three R ^e may be the same or different, and are preferably the same.

The amount of the aforementioned orthoesters is preferably 0.5 g or more, and more preferably 1 to 5 g, relative to EEMDA 1 g.

(Fifth step) In the fifth step, the EEMDE obtained in the fourth step is reacted with hydrogen to synthesize decahydro-1,4-ethyl bridge-5,8-methyl bridge naphthalene-2,3,6,7-tetracarboxylic acid. Tetramethyl acid (EMDE). The compound obtained in this step 5 is a tetraester compound represented by the aforementioned chemical formula (M-5) in which R ₇ is -CH ₂ CH ₂ -and is a novel compound.

This reaction can be performed, for example, by mixing EEMDE and a metal catalyst in a solvent, and stirring under heating in a hydrogen environment, if necessary. The reaction temperature at this time is preferably 0 to 150 ° C, and more preferably 10 to 120 ° C. The reaction pressure is preferably 0.1 to 20 MPa, and more preferably 0.1 to 5 MPa.

This reaction uses hydrogen. The amount of hydrogen used is preferably 0.8 to 100 mol, and more preferably 1 to 50 mol relative to EEMDE1 mol.

This reaction uses a metal catalyst. The metal catalyst used is not particularly limited as long as it can hydrogenate the olefin portion in the structure of EEMDE. For example: rhodium-based catalysts (rhodium carbon, Wilkinson complex, etc.) palladium-based catalysts (palladium Carbon, palladium-alumina, palladium-silicone, etc.), platinum-based catalysts (platinum-carbon, platinum-alumina, etc.), nickel-based catalysts (luny nickel catalyst, sponge nickel catalyst, etc.). A rhodium-based catalyst and a palladium-based catalyst are preferred, and a rhodium-based catalyst is more preferred.

The use amount of the aforementioned metal catalyst is, in terms of metal atoms, preferably 0.0001 to 1 mole, and more preferably 0.001 to 0.8 mole relative to EEMDE1 mole.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚)等。較佳為醇類、醯胺類、脂肪族烴類、及芳香族烴類。又，該等溶劑可單獨使用或混用二種以上。It is preferable to use a solvent in this reaction. The solvent to be used is not particularly limited as long as it does not hinder the reaction, for example: water, alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, etc.), ketones ( For example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amidines (for example: N, N-dimethyl Formamidine, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylisobutylamidine, etc.), ureas (N, N'-dimethylimidazolidone Etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, di

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol), and the like. Alcohols, amidines, aliphatic hydrocarbons, and aromatic hydrocarbons are preferred. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.1 to 100 g, and more preferably 1 to 50 g, relative to EEMDE 1 g.

(Step 6) In step 6, the dehydration reaction of EMDE obtained in step 5 was used to synthesize decahydro-1H, 3H-4,10-ethyl bridge-5,9-methaphthonaphtho [2,3 -c: 6,7-c '] difuran-1,3,6,8-tetraone (EMDA). The compound obtained in this step 6 is a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-4) in which R ₇ is -CH ₂ CH _2- .

This reaction can be carried out by, for example, a method of stirring EMDE in an organic solvent in the presence of an acid catalyst while heating. The reaction temperature at this time is preferably 50 to 130 ° C, and more preferably 80 to 120 ° C. The reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, such as: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid, etc .; Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel, zeolites, acid alumina, etc., preferably inorganic acids, organic sulfonic acids, and more preferably organic sulfonic acids. These acids can be used alone or in combination of two or more.

The amount of the aforementioned acid catalyst is preferably 0.001 to 0.5 mol, and more preferably 0.001 to 0.2 mol relative to EMDE1 mol.

This reaction is preferably carried out in a solvent. The solvent used is preferably an organic acid solvent such as formic acid, acetic acid, and propionic acid. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.1 to 100 g, and more preferably 1 to 10 g, relative to 1 g of EMDE.

The details of each reaction are explained according to the examples. Those with ordinary knowledge in the technical field can change the solvent, feed amount, reaction conditions, etc. After the completion of each reaction, it can be used for example: filtration, extraction, distillation, sublimation, re- The general methods such as crystallization and column chromatography are used to separate and purify the reaction products.

According to the present invention, a novel method for producing a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-9) which is a tetracarboxylic acid component having the structure of the aforementioned chemical formula (A-2) can be provided. The manufacturing method is described below.

The tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-9) can be synthesized by referring to Can. J. Chem. 1975, 53, 256, Tetrahedron Lett. 2003, 44, 561, and the like, for example, according to the reaction scheme shown below. Here, it is a tetracarboxylic dianhydride represented by the chemical formula (M-9) in which R ₄ is -CH _2- , that is, 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-form bridge The naphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone (BNDA) is taken as an example, but other tetracarboxylic dianhydrides can also be produced in the same manner.

式中，R₃₁ 、R₃₂ 各自獨立地為碳數1~10之烷基、或苯基，R₃₃ 、R₃₄ 各自獨立地為碳數1~10之烷基。[Chemical 48]

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ₃₃ and R ₃₄ are each independently an alkyl group having 1 to 10 carbon atoms.

(First step) In the first step, when synthesizing tetracarboxylic dianhydride (BNDA) of chemical formula (M-9) in which R ₄ is -CH _2- , cis-1,4-dichloro-2- Butene (DCB) is reacted with cyclopentadiene (CP) to synthesize 5,6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene (BCMN). When synthesizing the tetracarboxylic dianhydride of the formula (M-9) of R ₄ -CH ₂ CH _2- , as long as the cyclopentadiene (CP) is replaced with 1,3-cyclohexadiene, and DCB Just respond.

This reaction can be performed by, for example, mixing and stirring DCB and CP. The reaction temperature at this time is preferably 50 to 250 ° C, and more preferably 150 to 220 ° C. The reaction pressure is not particularly limited.

CP is a monomer of dicyclopentadiene (DCP). CP can be obtained quantitatively by heating DCP at 160 ~ 200 ° C. The CP used in this first step can also be used after it has occurred in the system by thermal decomposition of DCP. DCP is a compound shown in the scheme.

The use amount of the aforementioned CP is preferably 0.2 to 10 mol, and more preferably 0.5 to 5 mol relative to DCB1 mol.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚等)等。較佳為脂肪族烴類、及芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。This reaction may or may not use an organic solvent. The organic solvent used is not particularly limited as long as it does not interfere with the reaction, for example: aliphatic carboxylic acids (for example, formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example, methanesulfonic acid, trifluoromethanesulfonic acid Etc.), alcohols (for example: methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), ketones (for example: acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic Hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), ammonium (for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, diamine

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol, etc.) and the like. Preferred are aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

When an organic solvent is used, the amount of the aforementioned organic solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.2 to 10 g, and more preferably 0.3 to 5 g, relative to DCB 1 g.

(Second step) In the second step, the reaction between the BCMN obtained in the first step and the base is used for dechlorination and hydrogenation to synthesize 5,6-dimethylenebicyclo [2.2.1] hept-2-ene (CYDE).

This reaction can be performed by, for example, mixing and stirring BCMN and a base in a solvent. The reaction temperature at this time is preferably 0 to 150 ° C, and more preferably 20 to 120 ° C. The reaction pressure is not particularly limited.

This reaction uses a base. Bases used in this reaction, for example: secondary amines such as dibutylamine, piperidine, 2-methylpiperidine; tertiary amines such as triethylamine, tributylamine; pyridine, methylpyridine, dimethylaminopyridine Pyridines, etc .; Quinolines, such as quinoline, isoquinoline, methylquinoline; alkali metal hydrides such as sodium hydride, potassium hydride; alkali metals such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium third butoxide Alkoxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, preferably tertiary amines, Alkali metal alkoxide, alkali metal carbonate, alkali metal hydroxide. These bases can be used alone or in combination of two or more.

The amount of the aforementioned base to be used is preferably 1 to 20 moles, and more preferably 1.5 to 10 moles, relative to BCMN1 mole.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為水、醇類、醚類。又，該等溶劑可單獨使用或混用二種以上。This reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, such as: water, alcohols (for example, methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), aliphatic hydrocarbons ( For example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amidines (for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-formamide Pyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, diamine

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), fluorene (for example: dimethyl sulfene, etc.), fluorene (for example: Cyclops, etc.) and so on. Water, alcohols and ethers are preferred. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and is preferably 0.1 to 100 g, and more preferably 0.2 to 50 g, relative to 1 g of BCMN.

(3rd step) In the 3rd step, CYDE obtained in the 2nd step is reacted with dimethyl acetylene dicarboxylate (DMAD) to synthesize 1,4,5,8-tetrahydro-1,4-methylnaphthalene Dimethyl-6,7-dicarboxylic acid (CYME; in this case R ₃₁ and R ₃₂ are methyl). You may replace dimethyl acetylene dicarboxylate with another acetylene dicarboxylic acid diester mentioned later.

This reaction can be performed, for example, by mixing and stirring CYDE and DMD in a solvent. The reaction temperature at this time is preferably 0 to 150 ° C, and more preferably 20 to 120 ° C. The reaction pressure is not particularly limited.

This reaction uses an acetylene dicarboxylic acid diester such as DMAD. The acetylene dicarboxylic acid diester used is selected corresponding to the desired ester compound. Examples of the acetylene dicarboxylic acid diester used in this reaction include dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, dipropyl acetylene dicarboxylate, etc., preferably dimethyl acetylene dicarboxylate and acetylene dicarboxylic acid. Diethyl carboxylate. Diphenyl acetylene dicarboxylate can also be used. The two substituents bonded to acetylene may be the same or different.

The use amount of the aforementioned acetylene dicarboxylic acid diester such as DMAD is preferably 0.8 to 20 mol, and more preferably 1 to 10 mol, relative to CYDE1 mol.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚等)等。較佳為水、醇類、醚類、脂肪族烴類、芳香族烴類。又，該等溶劑可單獨使用或混用二種以上。This reaction is usually carried out in a solvent. The solvent to be used is not particularly limited as long as it does not interfere with the reaction, for example: water, alcohols (for example: methanol, ethanol, isopropanol, tertiary butanol, ethylene glycol, triethylene glycol, etc.), ketones (for example: Acetone, methyl ethyl ketone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amidines (for example: N, N-dimethylformamidine) Amines, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. diethyl ether, diisopropyl ether , Tetrahydrofuran, two

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), phenols (phenol, methylphenol, p-chlorophenol, etc.) and the like. Water, alcohols, ethers, aliphatic hydrocarbons, and aromatic hydrocarbons are preferred. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and it is preferably 0.2 to 200 g, and more preferably 0.3 to 100 g, relative to 1 g of CYME.

(Fourth step) In the fourth step, 1,4-dihydro-1,4-methylnaphthalene-6,7-dicarboxylic acid is synthesized by using the aromaticization reaction (oxidation reaction) of CYME obtained in the third step. Dimethyl ester (CYPDM).

This reaction can be performed by, for example, stirring CYME and an oxidizing agent for aromaticization in a solvent. The reaction temperature at this time is preferably -20 to 150 ° C, and more preferably 0 to 120 ° C. The reaction pressure is not particularly limited.

In this reaction, an oxidizing agent is used for aromatization. The oxidizing agent used is not particularly limited as long as it does not hinder the reaction, and for example, benzoquinones such as 2,3-dichloro-5,6-dicyano-p-benzoquinone and tetrachlorobenzoquinone can be used.

The amount of the aforementioned oxidant is preferably 0.5 to 10 moles, and more preferably 0.8 to 5 moles relative to CYME1 mole.

烷、四氫呋喃、環丙基甲醚等醚類；苯、甲苯、二甲苯等芳香族烴類；己烷、環己烷、庚烷、辛烷等脂肪族烴類；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等鹵化烴類；乙酸乙酯、乙酸丁酯等酯類；丙酮、甲乙酮、甲基異丁酮等，較佳為芳香族烴類、鹵化烴類、醚類、醇類、水。又，該等溶劑可單獨使用或混用二種以上。This reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it does not hinder the reaction, for example: water; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethyl Imidamines such as isobutylammonium amine; ureas such as N, N-dimethylimidazolidone; nitriles such as acetonitrile and propionitrile; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as tributanol; diisopropyl ether, di

Ethers such as alkane, tetrahydrofuran, cyclopropyl methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane; methylene chloride, chloroform, 1 2,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, butyl acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., preferably aromatic hydrocarbons, halogenated hydrocarbons, ethers Alcohol, alcohol, water. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and is preferably 1 to 100 g, and more preferably 2 to 50 g, relative to 1 g of CYME.

(Step 5) In step 5, CYPDM obtained in step 4 and methanol are reacted with carbon monoxide in the presence of a palladium catalyst and a copper compound to synthesize 1,2,3,4-tetrahydro-1,4- Tetramethylnaphthalene-2,3,6,7-tetracarboxylic acid tetramethyl ester (BNME; in this case R ₃₁ to R ₃₄ are methyl). It is also possible to replace methanol with another alcohol compound corresponding to the desired ester compound.

This reaction can be performed by, for example, mixing CYPDM and the alcohol corresponding to the desired ester compound, a palladium catalyst, and a copper compound in an organic solvent, and stirring under a carbon monoxide gas environment. The reaction temperature at this time is preferably -10 to 100 ° C, and more preferably -10 to 70 ° C. The reaction pressure is not particularly limited.

This reaction uses an alcohol compound. Alcohol compounds used in this reaction, such as: methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol Alcohol, triethylene glycol, and the like are preferably methanol, ethanol, n-propanol, and isopropanol, and more preferably methanol, ethanol, and isopropanol. These alcohol compounds may be used alone or in combination of two or more.

The amount of the aforementioned alcohol compound is preferably 0.1 to 200 g, and more preferably 1 to 100 g, relative to 1 g of CYPDM.

烷、1,2-亞甲基二氧化苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為脂肪族烴類、芳香族烴類、鹵化烴類、鹵化芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。In this reaction, organic solvents other than the aforementioned alcohols may be used. The organic solvent used is not particularly limited as long as it does not hinder the reaction, for example: formic acid, aliphatic carboxylic acids (for example: acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (for example: methanesulfonic acid, trifluoromethanesulfonic acid) Etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amidoamines (for example: N, N-dimethylformamide, N, N-dimethylformamide) Ethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N'-dimethylimidazolidone, etc.), ethers (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, diamine

Alkane, 1,2-methylene benzene dioxide, etc.), aromatic hydrocarbons (for example: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (for example: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride) , 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Amidines (for example: dimethyl fluorene, etc.), amidines (for example: cyclobutane, etc.), and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of organic solvents other than the aforementioned alcohols is preferably 0.1 to 200 g, and more preferably 1 to 100 g, relative to 1 g of CYPDM.

The palladium catalyst used in this reaction is not particularly limited as long as it contains palladium, for example: palladium halide such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; palladium inorganic acid salts such as palladium nitrate and palladium sulfate ; Palladium complexes such as bis (acetamidoacetone) palladium, bis (1,1,1-5,5,5-hexafluoroacetamidoacetone) palladium; palladium supported on carbon, oxidized Palladium carbon, palladium aluminum oxide, and the like obtained from a support such as aluminum are preferably palladium chloride and palladium carbon.

The amount of the palladium catalyst used is preferably 0.0001 to 0.2 mole, and more preferably 0.001 to 0.1 mole, relative to CYPDM1 mole.

For the copper compound used in this reaction, in the case where Pd (II) in the aforementioned palladium catalyst is reduced to Pd (0), there is no special restriction as long as it can oxidize Pd (0) to Pd (II), for example: copper compound , Iron compounds, etc., copper compounds are preferred. Specific examples of copper compounds used in this reaction include copper, copper acetate, copper propionate, copper n-butyrate, copper 2-methylpropionate, copper trimethylacetate, copper lactate, copper butyrate, and benzoic acid. Copper, copper trifluoroacetate, copper bis (acetamidoacetone) copper, copper (1,1,1-5,5,5-hexafluoroacetamidoacetone) copper, copper chloride, copper bromide, iodine Copper, copper nitrate, copper nitrite, copper sulfate, copper phosphate, copper oxide, copper hydroxide, copper triflate, copper p-toluenesulfonate, and copper cyanide. Specific examples of the iron compound include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, and iron (III) acetate. It is preferred to use a divalent copper compound, and even more preferred to use copper (II) chloride. Here, the "copper compound" is used in addition to various compounds in the meaning including a copper monomer. Moreover, these copper compounds can be used individually or in mixture of 2 or more types.

The amount of the aforementioned copper compound is preferably 4-50 mol, and more preferably 5-20 mol relative to CYPDM1 mol.

(Sixth step) In the sixth step, 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-methanonaphtho [2,3 is synthesized by the anhydrous reaction of BNME obtained in the fifth step. -c: 6,7-c '] difuran-1,3,6,8-tetraone (BNDA). The compound obtained in this sixth step is a tetracarboxylic dianhydride represented by the aforementioned chemical formula (M-9).

This reaction can be performed, for example, by heating BNME in an organic solvent in the presence of an acid catalyst while stirring, and the like. The reaction temperature at this time is preferably 50 to 130 ° C, and more preferably 80 to 120 ° C. The reaction pressure is not particularly limited.

This reaction uses an acid catalyst. The acid catalyst used in this reaction is not particularly limited as long as it is an acid, for example: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid and other inorganic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Organic sulfonic acids; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel, zeolites, acidic alumina, etc. It is preferable to use inorganic acids, organic sulfonic acids, and more preferably organic sulfonic acids. These acids can be used alone or in combination of two or more.

The amount of the aforementioned acid catalyst is preferably 0.001 to 0.5 mol, and more preferably 0.001 to 0.2 mol relative to BNME1 mol.

This reaction is preferably carried out in a solvent. The solvent used is preferably an organic acid solvent such as formic acid, acetic acid, and propionic acid. These solvents may be used alone or in combination of two or more.

The amount of the aforementioned solvent can be appropriately adjusted by using the uniformity and agitation of the reaction solution, and is preferably 0.1 to 100 g, and more preferably 1 to 10 g, relative to 1 g of BNME.

The details of each reaction are explained using examples, but those with ordinary knowledge in the technical field can change the solvent, feed amount, reaction conditions, etc. After the completion of each reaction, it can be used, for example: filtration, extraction, distillation, sublimation, Recrystallization, column chromatography and other general methods are used to isolate and purify the reaction product. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited to the following examples.

The evaluation of each of the following examples was performed by the following method.

＜ Evaluation of polyimide film ＞ [Total light transmittance] Using a UV-visible spectrophotometer / V-650DS (manufactured by Japan Spectroscopy), the total light transmittance of a polyimide film with a thickness of 10 μm (380nm ~ 780nm) was measured. Average transmittance).

[Tensile elastic modulus, elongation at break, breaking strength] A polyimide film was punched into a dumbbell shape according to IEC-540 (S). As a test piece (width: 4mm), TENSILON manufactured by ORIENTEC Corporation was used to clamp The head length was 30 mm and the tensile speed was 2 mm / min. The initial tensile elastic modulus, elongation at break point, and breaking strength were measured.

[Linear thermal expansion coefficient (CTE), Tg] A polyimide film with a thickness of 10 μm was cut into a strip with a width of 4 mm. As a test piece, TMA / SS6100 (manufactured by SII Technology Co., Ltd.) was used. The length is 15 mm, the load is 2 g, and the temperature rise rate is 20 ° C./min, and the temperature is raised to 500 ° C. From the obtained TMA curve, a linear thermal expansion coefficient of 100 ° C to 250 ° C was obtained. The inflection point of the TMA curve is defined as Tg (glass transition temperature).

[5% weight reduction temperature] A polyimide film having a film thickness of 10 μm was used as a test piece, and a thermal weight measuring device (Q5000IR) manufactured by TA Instruments was used, and the temperature was increased from 25 ° C. at a heating rate of 10 ° C./min in a nitrogen stream. To 600 ° C. From the obtained weight curve, a 5% weight reduction temperature was determined.

The abbreviations of the raw materials used in the following examples are as follows.

[Diamine component] DABAN: 4,4'-diaminobenzidine aniline PPD: p-phenylenediamine TFMB: 2,2'-bis (trifluoromethyl) benzidine 4,4'-ODA: 4, 4'-oxydiphenylamine TPE-R: 1,3-bis (4-aminophenoxy) benzene BAPB: 4,4'-bis (4-aminophenoxy) biphenyl tra-DACH: trans Formula-1,4-Diaminocyclohexane [tetracarboxylic acid component] TNDA: Tetradecyl-1H, 3H-4,12: 5,11: 6,10-Trimethyl bridge anthracene [2,3-c ： 6,7-c '] difuran-1,3,7,9-tetraketone BNDA: 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-methanonaphtho [2,3 -c: 6,7-c '] difuran-1,3,6,8-tetraketone DMADA: 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4, 12: 6,10-dimethylmethanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraketoneEMDAdx: (3aR, 4R, 5S, 5aR, 8aS , 9R, 10S, 10aS) -decahydro-1H, 3H-4,10-ethyl bridge-5,9-methyl bridge naphtho [2,3-c: 6,7-c '] difuran-1,3 , 6,8-tetraketone EMDAxx: (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -decahydro-1H, 3H-4,10-ethyl bridge-5,9-methyl bridge naphtho [ 2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone

[Solvent] NMP: N-methyl-2-pyrrolidone DMAc: N, N-dimethylacetamide

Table 1 shows the structural formulas of the tetracarboxylic acid component and the diamine component used in the examples and comparative examples.

【Table 1】

[Example S-1 (Synthesis of DMADA)]

於容量2L之反應容器裝入甲苯1500mL與對苯醌(BQ)153.3g(1.39mol)。然後保持溫度25-30℃，費時2小時滴加環戊二烯183.5g(2.78mmol)後，於25℃反應20小時。將反應液濃縮乾固，並於獲得之濃縮物中添加乙醇1490g，終夜攪拌。之後將固體過濾，以乙醇洗淨後，於60℃進行真空乾燥，獲得淡紅色固體227g。於獲得之淡紅色固體227g添加乙醇1350g，於80℃攪拌1小時，並將固體過濾。將過濾物以氯仿1080g溶解，添加活性碳10g並攪拌1小時。之後進行過濾，將濾液濃縮乾固，並將獲得之固體於60℃真空乾燥，獲得1,4,4a,5,8,8a,9a,10a-八氫-1,4：5,8-二甲橋蒽-9,10-二酮(DNBQ)之白色固體184g (¹ H-NMR分析測得純度100%、產率55.3%)。[Chemical 49]

A reaction container with a capacity of 2 L was charged with 1500 mL of toluene and 153.3 g (1.39 mol) of p-benzoquinone (BQ). After maintaining the temperature at 25-30 ° C, 183.5 g (2.78 mmol) of cyclopentadiene was added dropwise over 2 hours, and then the reaction was carried out at 25 ° C for 20 hours. The reaction solution was concentrated to dryness, and 1490 g of ethanol was added to the obtained concentrate, followed by stirring overnight. Thereafter, the solid was filtered, washed with ethanol, and then vacuum-dried at 60 ° C to obtain 227 g of a pale red solid. To 227 g of the obtained pale red solid, 1350 g of ethanol was added, and the mixture was stirred at 80 ° C. for 1 hour, and the solid was filtered. The filtrate was dissolved in 1080 g of chloroform, and 10 g of activated carbon was added and stirred for 1 hour. After filtering, the filtrate was concentrated to dryness, and the obtained solid was dried under vacuum at 60 ° C to obtain 1,4,4a, 5,8,8a, 9a, 10a-octahydro-1,4: 5,8-II 184 g of methoanthrene-9,10-dione (DNBQ) as a white solid (100% purity by ¹ H-NMR analysis, 55.3% yield).

The physical properties of DNBQ are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.29 (d, J = 8.5 Hz, 2H), 1.46 (d, J = 8.5 Hz, 2H), 2.87 (s, 2H), 3.36 (s, 2H ), 6.19 (t, J = 1.8Hz, 2H) CI-MS (m / z); 241 (M + 1)

In a reaction vessel having a capacity of 5 L, 100.5 g (31.7 mmol) of DNBQ, 1.5 L of methanol, and 1.5 L of tetrahydrofuran were added. Then, 30.0 g (60.3 mmol) of sodium borohydride was added at a temperature of 5 ° C for 1 hour, and then the reaction was performed at a temperature of 5 to 10 ° C for 7 hours. Next, 1 L of a saturated ammonium chloride aqueous solution was added dropwise at a temperature of 5 ° C, and then the temperature was raised to a temperature of 25 ° C. The white solid precipitated in the reaction solution was filtered, and the solvent was distilled off under reduced pressure. The precipitated white solid was filtered, and 1.5 L of ion-exchanged water was added to the obtained white solid, followed by stirring at 40 ° C for 1 hour. After that, the white solid was filtered, washed twice with 200 mL of ion-exchanged water, washed twice with 100 mL of ethyl acetate, and dried under vacuum to obtain 1,4,4a, 5,8,8a, 9,9a, 10,10a. -Decahydro-1,4: 5,8-dimethyl bridge anthracene-9,10-diol (DNHQ) as a white solid 84.2 g (100% purity and 82% yield by ¹ H-NMR analysis).

The physical properties of DNHQ are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 0.99 (d, J = 7.8 Hz, 1H), 1.16 (d, J = 7.8 Hz, 1H), 1.26-1.34 (m, 2H), 1.52 -1.62 (m, 2H), 2.34-2.42 (m, 2H), 2.77 (s, 2H), 2.85 (s, 2H), 2.91 (brs, 2H), 4.26 (s, 1H), 4.28 (s, 1H ), 6.04 (t, J = 1.8 Hz, 2H), 6.09 (t, J = 1.8 Hz, 2H) CI-MS (m / z); 245 (M + 1)

In a reaction vessel with a capacity of 5 L, 87.0 g (356 mmol) of DNHQ, 4.3 g (35.2 mmol) of N, N-dimethylaminopyridine, and 1740 g of pyridine were added, and the temperature was cooled to 5 ° C. Then, 87.0 g (760 mmol) of methanesulfonyl chloride was added dropwise over a period of 20 minutes, and then the temperature was raised to 25 ° C, and the reaction was performed at the same temperature for 9 hours. Then, 2500 g of ion-exchanged water was added dropwise, and the precipitated white solid was filtered. The obtained white solid was washed 5 times with 200 mL of 10% hydrochloric acid, 200 mL of 10% sodium bicarbonate aqueous solution, 200 mL of ion-exchanged water, and dried under vacuum. 128.9 g of the obtained white solid was dissolved in 2800 g of ethyl acetate, and dried (dehydrated) with 35 g of anhydrous magnesium sulfate. Then, this ethyl acetate solution was passed into a silica gel column, and the solvent was distilled off with an evaporator to obtain 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydromethanesulfonic acid. 124.5 g of -1,4: 5,8-dimethyl bridge anthracene-9,10-diester (DNCMS) as a white solid (purity 99% by ¹ H-NMR analysis, yield 87.4%).

The physical properties of DNCMS are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 1.18 (d, J = 8.3 Hz, 1H), 1.32 (d, J = 8.2 Hz, 1H), 1.39-1.42 (m, 2H), 2.00 -2.15 (m, 2H), 2.81 (s, 2H), 2.85-2.90 (m, 2H), 2.97 (s, 2H), 3.22 (s, 6H), 4.10-4.20 (m, 2H), 6.23 (s , 2H), 6.27 (s, 2H) CI-MS (m / z); 401 (M + 1)

A reaction vessel having a capacity of 1 L was charged with 364 g of methanol, 62 g of chloroform, 136 g (1011 mmol) of copper (II) chloride, and 6 g (33.7 mmol) of palladium chloride, and stirred. After replacing the gas environment in the system with carbon monoxide, a solution prepared by dissolving 27 g (67.3 mmol) of DNCMS in 178 g of chloroform was added dropwise over 3 hours, and reacted at 20-25 ° C for 4 hours. Next, after replacing the gas environment in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 621 g of chloroform was added. Repeat the same operation twice more. And, the insoluble matter was removed from the obtained tea green suspension by filtration. The obtained solution was washed three times with 324 g of a saturated sodium bicarbonate aqueous solution and three times with 324 g of purified water, and then 2.7 g of anhydrous magnesium sulfate and 2.7 g of activated carbon were added to the organic layer and stirred. The solution was filtered and concentrated under reduced pressure to obtain 51 g of a white solid. Next, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate = 10: 1 (volume ratio)) to obtain 9,10-bis ((methylsulfonyl) oxy) tetradecyl- 27 g of a white solid of 1,4: 5,8-dimethyl bridge anthracene-2,3,6,7-tetracarboxylic acid ester (DNMTE) was analyzed by HPLC (purity: 97.1 pa%, yield: 64.4%).

The physical properties of DNMTE are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.49 (d, J = 10 Hz, 2H), 2.31 (d, J = 10 Hz, 2H), 2.62-2.67 (m, 2H), 2.69 (s, 2H ), 2.87 (s, 4H), 3.06 (s, 6H), 3.19 (s, 2H), 3.32 (s, 2H), 3.64 (s, 6H), 3.66 (s, 6H), 4.98-5.12 (m, 2H) CI-MS (m / z); 637 (M + 1)

A 500-mL reaction container was charged with 6.4 g (86.8 mmol) of lithium carbonate and 130 g of N, N'-dimethylformamide, and the temperature was raised to 150 ° C. Then, a mixed solution of 27.6 g (42.1 mol) of DNMTE and 130 g of N, N'-dimethylformamide was added dropwise over 1 hour, and reacted at the same temperature for 15 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure to obtain 22.4 g of a white solid. Next, purification by silica gel chromatography (developing solvent; hexane: ethyl acetate = 10: 1 (volume ratio)) was performed, and then recrystallization (solvent ratio; toluene / heptane = 2: 3) was performed. Refined to obtain 1,2,3,4,4a, 5,6,7,8,9a-decahydro-1,4: 5,8-dimethylmethanthracene-2,3,6,7-tetracarboxylic acid Tetramethyl ester (DMHAE) was 13.9 g of a white solid (purity: 95.1 pa% by HPLC analysis, yield: 72.2%).

The physical properties of DMHAE are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.36 (d, J = 10 Hz, 1 H), 1.56 (d, J = 10 Hz, 1 H), 2.05 (d, J = 10 Hz, 1 H), 2.29 (d , J = 10Hz, 1H), 2.56 (s, 2H), 2.83 (s, 2H), 2.90 (d, J = 1.6Hz, 2H), 3.05 (s, 2H), 3.07 (d, J = 1.6Hz, 2H), 3.61 (s, 6H), 3.65 (s, 6H), 5.10 (s, 2H) CI-MS (m / z); 445 (M + 1)

A 300 mL reaction vessel was charged with 68 mL of toluene and 7.3 g (31.9 mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the temperature was raised to 80 ° C. A solution prepared by dissolving 13.5 g of DMHAE (30.4 mmol) in 200 mL of toluene was added dropwise, and reacted for 8 hours. After the reaction was completed, the reaction solution was concentrated, and 130 mL of chloroform was added to the concentrate to obtain a black tea-colored suspension. It was then filtered to separate the dark red and black filter and filtrate. The filtrate was washed three times with 100 mL of a saturated sodium bicarbonate aqueous solution, and then 12 g of anhydrous magnesium sulfate was added to the obtained organic layer to dehydrate it. After filtering, the filtrate was concentrated to dryness to obtain 5.6 g of a red-brown solid. Further, 100 mL of chloroform was added to the dark red and black filter, and the same operation was performed to obtain 4.0 g of a reddish brown solid. 9.6 g of the obtained red-brown solid was purified by recrystallization (solvent ratio; toluene: heptane = 1: 7) to obtain 1,2,3,4,5,6,7,8-octahydro-1 , 4: 5,8-Dimethanthracene-2,3,6,7-tetracarboxylic acid tetramethyl ester (DMAME), 7.4 g (purity 99.9pa%, 56.6% yield by HPLC analysis).

The physical properties of DMAME are as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.80 (d, J = 9.6 Hz, 2H), 2.43 (d, J = 9.6 Hz, 2H), 2.68 (d, J = 1.6 Hz, 4H), 3.53 (s, 4H), 3.67 (s, 12H), 7.06 (s, 2H) CI-MS (m / z); 442 (M + 1)

A reaction container with a capacity of 100 mL was charged with 5.27 g (11.9 mmol) of DMAME, 26.3 g of formic acid, and 47 mg (0.24 mmol) of p-toluenesulfonic acid monohydrate, and reacted at a temperature of 98 ° C for 30 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 30 g of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The obtained suspension was filtered, and the obtained solid was washed with 30 g of toluene, and then vacuum-dried at 80 ° C. to obtain 4.0 g of a milky white solid. Then it is recrystallized with acetic anhydride and then recrystallized with N, N'-dimethylacetamide to obtain 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4 , 12: 6,10-dimethylmethanthracene [2,3-c: 6,7-c '] difuran-1,3,7,9-tetraone (DMADA) 3.28 g ( ¹ H -NMR analysis measured 98.3% purity and 77.3% yield).

The physical properties of DMADA are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 1.61 (d, J = 10.8 Hz, 2H), 1.81 (d, J = 10.8 Hz, 2H), 3.04 (s, 2H), 3.04 (s , 2H), 3.76 (s, 4H), 7.39 (s, 2H) CI-MS (m / z); 351 (M + 1)

[Example S-2-1 (Synthesis of EMDAdx)]

於容量3L之高壓釜中裝入順式-5-降莰烯-內向-2,3-二羧酸酐(endo -NA) 600g(3.66mol)，然後裝入2,6-二丁基羥基甲苯1.20g。將系內進行氮氣取代後，於溫度-25℃添加1,3-丁二烯221g(4.09mol)，於溫度150-160℃反應一晩，獲得白色固體760g。將以上之操作再重複2次，獲得白色固體2258g(產率36%)。然後，於獲得之白色固體2258g添加甲苯9.7L，於溫度102℃加熱攪拌，使固體溶解。於同溫度攪拌10分鐘後，添加庚烷2.6L，冷卻到室溫並攪拌一晩，將析出之固體過濾。將獲得之固體以庚烷2.6L洗淨後，於40℃進行5小時真空乾燥，獲得白色固體691g。[Chemical 50]

In a 3L autoclave, 600g (3.66mol) of cis-5-norbornene-inward-2,3-dicarboxylic anhydride ( endo- NA) was charged, and then 2,6-dibutylhydroxytoluene was charged. 1.20g. After the system was replaced with nitrogen, 221 g (4.09 mol) of 1,3-butadiene was added at a temperature of -25 ° C, and the mixture was reacted at a temperature of 150-160 ° C for one night to obtain 760 g of a white solid. The above operation was repeated two more times to obtain 2258 g of a white solid (yield 36%). Then, 9.7 L of toluene was added to 2258 g of the obtained white solid, and the mixture was heated and stirred at a temperature of 102 ° C. to dissolve the solid. After stirring at the same temperature for 10 minutes, 2.6 L of heptane was added, cooled to room temperature and stirred overnight, and the precipitated solid was filtered. The obtained solid was washed with 2.6 L of heptane, and then vacuum-dried at 40 ° C. for 5 hours to obtain 691 g of a white solid.

A reaction container having a capacity of 5 L was charged with 691 g of the obtained white solid and 2.1 L of toluene. After heating and stirring at a temperature of 98 ° C, 1.1 L of heptane was added and cooled to room temperature, followed by stirring for a while. The precipitated solid was filtered, washed with 1.1 L of heptane, and vacuum-dried at 40 ° C for 3 hours to obtain (3aR, 4S, 9R, 9aS) -3a, 4,4a, 5,8,8a, 9,9a -Octahydro-4,9-methanonaphtho [2,3-c] furan-1,3-dione (OMNAdx) as a white solid 634 g (purity 99.1% by ¹ H-NMR analysis, yield 26%) ).

The physical properties of OMNAdx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.50 (d, J = 11 Hz, 1H), 1.52-1.63 (m, 3H), 1.78-1.87 (m, 2H), 2.12 (d, J = 11Hz , 1H), 2.24-2.35 (m, 2H), 2.54-2.59 (m, 2H), 3.42 (dd, J = 2.1Hz, J = 3.5Hz, 2H), 5.83-5.91 (m, 2H) CI-MS (m / z); 219 (M + 1)

In a reaction vessel with a capacity of 20 L, 560 g (2.54 mol) of OMNAdx and 9.5 L of dichloromethane were added. While cooling to a temperature of -55 to -43 ° C, a solution obtained by dissolving 496 g (3.1 mol) of bromine in 4.9 L of dichloromethane was added dropwise and reacted for 1 hour. After the reaction, the solvent was removed by an evaporator, and 600 mL of heptane was added to the obtained solid, followed by stirring. The white solid was filtered, washed with 4.5 L of heptane, and dried under reduced pressure at 40 ° C. to obtain (3aR, 4S, 9R, 9aS) -6,7-dibromodecahydro-4,9-methacylnaphthalene. [2,3-c] furan-1,3-dione (DBDNAdx) was 805 g of a white solid (purity was 100% by ¹ H-NMR analysis, yield was 78%).

The physical properties of DBDNAdx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.52-1.76 (m, 2H), 1.88-2.05 (m, 4H), 2.05-2.24 (m, 2H), 2.57 (brs, 2H), 3.48 ( t, J = 2.5 Hz, 2H), 4.30 (ddd, J = 3.6 Hz, J = 5.4 Hz, J = 12.5 Hz, 1H), 4.68 (dt, J = 3.3 Hz, J = 3.5 Hz, 1H) CI- MS (m / z); 379 (M + 1)

In a reaction vessel with a capacity of 2 L, 130 g (1.33 mol) of maleic anhydride and 100 g (264.5 mmol) of DBDNAdx were added, and reacted at a temperature of 187 ° C for 2 hours. After the reaction was completed, the temperature was cooled to 100 ° C, and 400 mL of toluene was added. After cooling to about room temperature, the precipitated solid was filtered, washed with toluene, and vacuum-dried at 60 ° C to obtain (3aR, 4R, 5S, 5aR, 8aS, 9R, 10S, 10aS) -3a, 4,4a, 5,5a, 8a, 9,9a, 10,10a-Decahydro-1H, 3H-4,10-Ethyl bridge-5,9-methyl bridge naphtho [2,3-c: 6,7-c '] 75 g of a gray solid of difuran-1,3,6,8-tetraone (EEMDAdx) (purity: 98.4% by ¹ H-NMR analysis, yield: 89%).

The physical properties of EEMDAdx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.04 (d, J = 10.8 Hz, 1H), 1.82 (s, 2H), 2.30 (d, J = 10.8 Hz, 1H), 2.62 (s, 2H ), 3.20 (s, 2H), 3.39 (m, 2H), 3.42 (d, J = 2.1Hz, J = 3.4Hz, 2H), 6.20 (dd, J = 3.2Hz, J = 4.5Hz, 2H) CI -MS (m / z); 314 (M + 1)

75 g (239 mmol) of EEMDAdx, 152 g of trimethyl orthoformate, 1500 g of methanol, and 22.5 g of concentrated sulfuric acid were added to a reaction vessel having a capacity of 2 L, and the reaction was carried out at a temperature of 63 ° C. for 23 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, 600 g of a saturated sodium bicarbonate aqueous solution was added to the concentrated residue, and the mixture was extracted with 500 g of chloroform. The organic layer was washed twice with 200 g of water, dried (dehydrated) with anhydrous magnesium sulfate (MgSO ₄ ), and then filtered, and the filtrate was concentrated under reduced pressure to obtain 80.7 g of a solid. Then crystallization using 150g of toluene and 450g of heptane was carried out to obtain (1R, 4S, 5R, 6S, 7R, 8S, 10S, 11R) -1,4,4a, 5,6,7,8,8a-eight 75g of hydrogen-1,4-ethyl bridge-5,8-methacylnaphthalene-6,7,10,11-tetracarboxylic acid tetramethyl ester (EEMDEdx) as a white solid (purity 100% by ¹ H-NMR analysis, 77% yield).

The physical properties of EEMDEdx are as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 0.81 (d, J = 11 Hz, 1H), 2.29 (s, 2H), 2.43 (s, 2H), 2.58 (d, J = 11 Hz, 1H), 2.86 (t, J = 2.0 Hz, 2H), 3.00 (brs, 2H), 3.05 (s, 2H), 3.57 (s, 6H), 3.65 (s, 6H), 6.28 (dd, J = 3.3Hz, J = 4.6Hz, 2H) CI-MS (m / z); 407 (M + 1)

In a reaction container having a capacity of 200 mL, 3 g of EEMDEdx 6 g (14.8 mmol), 120 g of methanol, and 10% rhodium-carbon catalyst (manufactured by N.E. Chemcat, 50 wt% water-containing product) were added. After the system was replaced with hydrogen, the hydrogen was pressurized to 0.9 MPa and reacted at an internal temperature of 80 ° C for 4 hours. After the reaction was completed, the reaction product was washed with 100 mL of N, N'-dimethylformamide and taken out. The obtained reaction suspension was filtered through celite and concentrated under reduced pressure to obtain a white solid. This operation was repeated 7 times to obtain 41.2 g of a white solid (99.9% purity and 97% yield by GC analysis). Next, purification was performed using a silica gel column (developing solvent; hexane / ethyl acetate = 3/1 (v / v)) to obtain (1R, 2R, 3S, 4S, 5R, 6S, 7R, 8S) -decahydro 35 g of white solid -1,4-ethyl bridge-5,8-methacylnaphthalene-2,3,6,7-tetracarboxylic acid tetramethyl ester (EMDEdx) (100% purity by GC analysis, 83% yield) ).

The physical properties of EMDEdx are as follows. ¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.25 (d, J = 11 Hz, 1H), 1.49 (d, J = 9.0 Hz, 2H), 1.79 (d, J = 9.0 Hz, 2H), 2.00 (s, 2H), 2.14 (s, 2H), 2.24 (d, J = 11 Hz, 1H), 2.51 (s, 2H), 2.90 (s, 2H), 3.02 (t, J = 2.0 Hz, 2H), 3.63 (s, 6H), 3.64 (s, 6H) CI-MS (m / z); 409 (M + 1)

In a reaction container with a capacity of 300 mL, 30 g (73.4 mmol) of EMDEDx, 150 g of formic acid, and 280 mg (1.47 mmol) of p-toluenesulfonic acid monohydrate were added, and reacted at a temperature of 95 ° C to 99 ° C for 16 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 72 mL of toluene was added to the concentrate. This operation was repeated 6 times, and formic acid was almost completely distilled off. The obtained suspension was filtered, and the obtained solid was washed with 35 mL of toluene, and then dried under vacuum at 80 ° C. to obtain 23.4 g of a gray solid. Afterwards, it was recrystallized by using acetic anhydride and N, N'-dimethylacetamide to obtain (3aR, 4R, 5S, 5aR, 8aS, 9R, 10S, 10aS) -decahydro-1H, 3H-4, 10-Ethyl-5,9-methanonaphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone (EMDAdx) as a white solid 18.9g ( ¹ H-NMR analysis measured a purity of 98.5% and a yield of 80%).

The physical properties of EMDAdx are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 1.17 (d, J = 9.9 Hz, 2H), 1.48 (d, J = 12 Hz, 1H), 1.45-1.68 (m, 4H), 2.04- 2.14 (m, 3H), 2.69 (s, 2H), 3.29 (s, 2H), 3.55 (dd, J = 1.2Hz, J = 2.1Hz, 2H) CI-MS (m / z); 317 (M + 1)

[Example S-2-2 (Synthesis of EMDAxx)]

於3L之高壓釜內裝入順式-5-降莰烯-外向-2,3-二羧酸酐(exo -NA)600g(3.66mol)、2,6-二丁基羥基甲苯300mg。將系內進行氮氣取代後，於內溫-25℃添加1,3-丁二烯319g(5.91mol)，於反應溫度140~166℃進行35小時攪拌，獲得白色固體866.2g(產率58%)。然後將獲得之白色固體866.2g以甲苯再結晶，獲得(3aR,4R,9S,9aS)-3a,4,4a,5,8,8a,9,9a-八氫-4,9-甲橋萘并[2,3-c]呋喃-1,3-二酮(OMNAxx)之白色結晶359g(¹ H-NMR分析測得純度100%、產率45%)。[Chemical 51]

A 3L autoclave was charged with 600 g (3.66 mol) of cis-5-norbornene-exo-2,3-dicarboxylic anhydride ( exo- NA) and 300 mg of 2,6-dibutylhydroxytoluene. After the inside of the system was replaced with nitrogen, 319 g (5.91 mol) of 1,3-butadiene was added at an internal temperature of -25 ° C, and the mixture was stirred at a reaction temperature of 140 to 166 ° C for 35 hours to obtain 866.2 g of a white solid (yield 58%). ). Then 866.2 g of the obtained white solid was recrystallized from toluene to obtain (3aR, 4R, 9S, 9aS) -3a, 4,4a, 5,8,8a, 9,9a-octahydro-4,9-methynaphthalene 359 g of white crystals of [2,3-c] furan-1,3-dione (OMNAxx) (purity was 100% by ¹ H-NMR analysis, and yield was 45%).

The physical properties of OMNAxx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.19 (d, J = 12 Hz, 1 H), 1.52-1.63 (m, 2H), 1.73-1.82 (m, 2H), 1.89 (d, J = 12 Hz , 1H), 2.27-2.40 (m, 2H), 2.56 (t, J = 1.2Hz, 2H), 2.98 (d, J = 1.2Hz, 2H), 5.80-5.92 (m, 2H) CI-MS (m / z); 219 (M + 1)

A reaction container having a capacity of 3 L was charged with 120 g (550 mmol) of OMNAxx and 2.2 L of dichloromethane. While cooling to a temperature of -65 to -60 ° C, a solution obtained by dissolving 105.4 g (660 mmol) of bromine in 200 mL of dichloromethane was added dropwise over 2 hours, and reacted for 1 hour. This operation is performed twice. The reaction solution was collected in two portions and concentrated by an evaporator to obtain a light brown solid. To the obtained light brown solid, 1.5 L of heptane was added and filtered. The filtered solid was washed with 500 mL of heptane and dried under vacuum to obtain (3aR, 4R, 9S, 9aS) -6,7-dibromodecahydro-4,9-methanonaphtho [2,3- c] 313 g of furan-1,3-dione (DBDNAxx) as a white solid (100% purity and 75% yield by ¹ H-NMR analysis). The filtrate was concentrated under reduced pressure, washed with 500 mL of heptane, and dried under vacuum to obtain 78.1 g of DBDNAxx as a white solid (100% purity and 19% yield by ¹ H-NMR analysis).

The physical properties of DBDNAxx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.28 (d, J = 12 Hz, 1H), 1.62 (q, J = 12 Hz, 1H), 1.84-2.24 (m, 5H), 2.59 (s, 2H ), 3.03 (dd, J = 7.3 Hz, J = 23 Hz, 2H), 4.32 (ddd, J = 3.3 Hz, J = 5.5 Hz, J = 12 Hz, 1H), 4.73 (dd, J = 3.0 Hz, J = 7.0Hz, 1H) CI-MS (m / z); 379 (M + 1)

In a reaction vessel with a capacity of 2 L, 259 g (2.64 mol) of maleic anhydride and 200 g (529 mmol) of DBDNAxx were added, and reacted at a reaction temperature of 190 ° C for 2 hours. After the reaction was completed, the temperature was cooled to 100 ° C, and 900 mL of toluene was added. After cooling to room temperature, the precipitated solid was separated by filtration. The obtained solid was washed with 900 mL of toluene, and then dried under reduced pressure at 60 ° C for 3 hours to obtain (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -3a, 4, 4a, 5 , 5a, 8a, 9,9a, 10,10a-decahydro-1H, 3H-4,10-ethyl bridge-5,9-methyl bridge naphtho [2,3-c: 6,7-c '] 140.2 g of a light brown solid of furan-1,3,6,8-tetraketone (EEMDAxx) (97.2% purity and 82% yield by ¹ H-NMR analysis).

Further, the same operation was performed on 180 g (476 mmol) of DBDNAxx to obtain 139.2 g of a light brown solid of EEMDAxx ( ¹ H-NMR purity 98.9%, yield 92%).

The physical properties of EEMDAxx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 0.59 (d, J = 12 Hz, 1H), 2.01 (s, 2H), 2.12 (d, J = 12 Hz, 1H), 2.55 (s, 2H), 2.98 (d, J = 1.4 Hz, 2H), 3.20-3.30 (m, 4H), 6.20 (dd, J = 3.1 Hz, J = 4.4 Hz, 2H) CI-MS (m / z); 314 (M + 1)

A reaction vessel with a capacity of 20 L was charged with EEMDAxx254.9 g (794.8 mmol), 10 L of methanol, 533 g of trimethyl orthoformate, and 63 g of concentrated sulfuric acid, and stirred at a temperature of 61 to 67 ° C. for 79 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure to obtain 513 g of a gray solid. The obtained solid was dissolved in 3256 g of chloroform, and 1700 g of a 7% by weight aqueous sodium hydrogen carbonate solution was added dropwise. To the separated organic layer were added 31.6 g of anhydrous magnesium sulfate and 26.8 g of activated carbon, and the mixture was stirred at room temperature for 1 hour, and then filtered. The filtrate was washed with 322 g of chloroform and concentrated under reduced pressure to obtain 325.3 g of a gray solid. The obtained gray solid was then recrystallized from methanol to obtain (1R, 4S, 5R, 6R, 7S, 8S, 10S, 11R) -1,4,4a ,, 6,7,8,8a-octahydro-1, 294.9 g of 4-ethyl bridge-5,8-methacylnaphthalene-6,7,10,11-tetracarboxylic acid tetramethyl ester (EEMDExx) as a white solid (100% purity and 91% yield by GC analysis).

The physical properties of EEMDExx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.55 (d, J = 11 Hz, 1H), 1.61 (s, 2H), 2.29 (d, J = 11 Hz, 1H), 2.43 (s, 2H), 2.62 (d, J = 1.9 Hz, 2H), 2.97 (s, 2H), 3.03 (s, 2H), 3.58 (s, 6H), 3.60 (s, 6H), 6.23 (dd, J = 3.2Hz, J = 4.6Hz, 2H) CI-MS (m / z); 407 (M + 1)

In an autoclave with a capacity of 3 L, EEMDExx 98.2 g (242 mmol) and 1,720 g of methanol were added, and 49.1 g of 10% rhodium-carbon catalyst (manufactured by N.E. Chemcat, 50% water-containing product) was added. After the system was replaced with hydrogen, the hydrogen was pressurized to 0.9 MPa and reacted at an internal temperature of 80 ° C for 4 hours. After the reaction was completed, the precipitated solid was dissolved with 3235 g of N, N'-dimethylformamide, and the reaction product was taken out, filtered through celite, and the catalyst was removed. This operation was performed twice more for EEMDExx 97.3 g (239 mmol). Then, all the filtrates were combined and concentrated under reduced pressure to obtain 289.1 g of a gray solid. The obtained gray solid was recrystallized from 700 g of chloroform and 4373 g of heptane to obtain (1R, 2R, 3S, 4S, 5R, 6R, 7S, 8S) -decahydro-1,4-ethyl bridge-5,8-methyl bridge Naphthalene-2,3,6,7-tetracarboxylic acid tetramethyl ester (EMDExx) was a fine gray solid 283.0 g (purity 99.9pa% and yield 96% by GC analysis).

The physical properties of EMDExx are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.52 (d, J = 9.0 Hz, 2H), 1.58 (s, 2H), 1.76 (d, J = 9.0 Hz, 2H), 1.95-2.10 (m , 4H), 2.52 (s, 2H), 2.71 (d, J = 1.6Hz, 2H), 2.84 (s, 2H), 3.63 (s, 6H), 3.64 (s, 6H) CI-MS (m / z ); 409 (M + 1)

EMDExx 282.0 g (689.7 mmol), formic acid 1410 g, and p-toluenesulfonic acid monohydrate 3.28 g (17 mmol) were added to a reaction vessel with a capacity of 3 L, and the reaction was carried out at a temperature of 95 ° C to 97 ° C for 19 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 700 mL of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The obtained suspension was filtered, and the obtained solid was washed with 490 mL of toluene, and then dried under vacuum at 80 ° C. to obtain 219.6 g of a gray solid. Thereafter, recrystallization using acetic anhydride and recrystallization using N, N'-dimethylformamide were performed to obtain (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -decahydro -1H, 3H-4,10-ethyl bridge-5,9-methyl bridge naphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone (EMDAxx) 175.9 g of a white solid (99.4% purity and 96% yield by ¹ H-NMR analysis).

Furthermore, 150 g of the obtained EMDAxx was refined under the sublimation conditions of 250 to 290 ° C./5Pa to obtain 146 g of a white solid of EMDAxx (purity was 100% by ¹ H-NMR analysis, and the recovery was 97.6%).

The physical properties of EMDAxx are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 0.98 (d, J = 13 Hz, 1H), 1.15 (d, J = 9.4 Hz, 2H), 1.57 (d, J = 9.4 Hz, 2H) , 1.81 (s, 2H), 1.91 (d, J = 13Hz, 1H), 2.17 (s, 2H), 2.63 (s, 2H), 3.04 (s, 2H), 3.19 (s, 2H) CI-MS ( m / z); 317 (M + 1)

[Example S-3 (Synthesis of BNDA)]

於容量1L之高壓釜中裝入順式-1,4-二氯-2-丁烯233g(1.76mol)、二環戊二烯245g(1.96mol)、甲苯176mL。將系內進行氮氣取代後，於溫度180℃反應5小時。打開高壓釜，取出反應物並濃縮。[Chemical 52]

A 1-liter autoclave was charged with 233 g (1.76 mol) of cis-1,4-dichloro-2-butene, 245 g (1.96 mol) of dicyclopentadiene, and 176 mL of toluene. After replacing the inside of the system with nitrogen, the reaction was carried out at a temperature of 180 ° C for 5 hours. The autoclave was opened, the reaction was removed and concentrated.

Then, an autoclave having a capacity of 1 L was charged with 149 g (1.13 mol) of cis-1,4-dichloro-2-butene, 156 g (1.25 mol) of dicyclopentadiene, and 112 mL of toluene. After replacing the nitrogen in the system, the reaction was carried out at a temperature of 180 ° C for 5 hours. The autoclave was opened, the reaction was removed and concentrated.

The reactants (concentrated residues) obtained from the total of two reactions were combined (a total of 942 g) and distilled under reduced pressure to obtain 5,6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene (BCMN). Light brown liquid 396.8 g (purity 74.7%, yield 65% by GC analysis).

The physical properties of BCMN are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.37 (d, J = 8.4 Hz, 1H), 1.56 (d, J = 8.4 Hz, 1H), 2.55-2.67 (m, 2H), 3.06-3.17 (m, 4H), 3.47 (dd, J = 5.8Hz, J = 10Hz, 2H), 6.25 (t, J = 2.0Hz, 2H) CI-MS (m / z); 191 (M + 1)

In a reaction vessel having a capacity of 5 L, 307 g (4.65 mol) of an 85 wt% sodium hydroxide aqueous solution, 2.3 L of ethanol, and 396.8 g (1.55 mol) of BCMN were added, and the mixture was heated and stirred at a reaction temperature of 78 ° C for 41 hours. After the reaction was completed, the obtained suspension was filtered. Then, the filtrate was cooled to a temperature of 10 ° C, and 120 g of concentrated sulfuric acid was added dropwise while cooling to a temperature of 10 to 20 ° C to obtain a suspension. The obtained suspension was filtered, and the filtrate was distilled under reduced pressure at 55-58 ° C / 290-300mmHg to obtain an ethanol solution of 5,6-dimethylmethylenebicyclo [2.2.1] hept-2-ene (CYDE). 2424g.

The physical properties of CYDE are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.57 (d, J = 8.2 Hz, 1H), 1.77 (d, J = 8.2 Hz, 1H), 3.30 (d, J = 1.8 Hz, 2H), 4.95 (s, 2H), 5.16 (s, 2H), 6.19 (s, 2H) CI-MS (m / z); 119 (M + 1)

In a reaction container with a capacity of 10 L, 2424 g of the obtained ethanol solution of CYDE and 264.3 g (1.86 mol) of dimethyl acetylene dicarboxylate were added, and the reaction was performed at a reaction temperature of 70 to 78 ° C. for 17 hours. After the reaction was completed, the ethanol was distilled off under reduced pressure to obtain 369.3 g of a brown liquid. Next, it was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 15: 1 (volume ratio)) to obtain a brown liquid containing 1,4,5,8-tetrahydro-1,4. -Dimethylnaphthalene-6,7-dicarboxylate (CYME) fraction (1) 126g (purity measured by GC analysis 85.6pa%) and fraction (2) 177g (purity measured by GC analysis 50.9pa%) The two fractions [total yield (BCMN-based yield) 49%].

The physical properties of CYME are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.98 (d, J = 0.8 Hz, 2H), 2.85-3.02 (m, 2H), 3.21-3.40 (m, 4H), 3.76 (s, 6H) , 6.76 (t, J = 1.8Hz, 2H) CI-MS (m / z); 261 (M + 1)

In a reaction container with a capacity of 3 L, 126 g of CYME-containing fraction (1) (purity 85.6 pa%; 414.4 mmol), 1.3 m of dichloromethane, and 2,3-dichloro-5,6-di were added under an argon atmosphere. 138 g (607.9 mmol) of cyano p-benzoquinone was reacted at 20 ° C for 7 hours.

In a reaction container with a capacity of 3 L, 177 g of a CYME-containing fraction (2) (purity 50.9 pa%; 346.1 mmol), 890 mL of dichloromethane, and 2,3-dichloro-5,6- were added under an argon atmosphere. 97.7 g (430.4 mmol) of dicyano-p-benzoquinone were reacted at 20 ° C for 7 hours.

The reactants obtained from the two reactions were combined and concentrated under reduced pressure to obtain 457.4 g of a brown liquid. Then, it was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 15: 1 (volume ratio)) to obtain 248.9 g of a red oily substance. This oily substance was dissolved in 2 L of ethyl acetate, washed three times with 500 mL of a saturated sodium bicarbonate aqueous solution, and then washed with 500 mL of a saturated saline solution, dried over sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure to obtain 146 g of a red oily substance of dimethyl 1,4-dihydro-1,4-methylnaphthalene-6,7-dicarboxylic acid (CYPDM) (purity: 99.1 pa% by GC analysis, yield: 74%).

The physical properties of CYPDM are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 2.26 (d, J = 7.6 Hz, 1H), 2.36 (d, J = 7.6 Hz, 1H), 3.85 (s, 6H), 3.94 (t, J = 1.8Hz, 2H), 6.77 (t, J = 1.8Hz, 2H), 7.56 (s, 2H) CI-MS (m / z); 259 (M + 1)

A 500 mL reaction container was charged with 135 g of methanol, 41 g of chloroform, 52 g (387 mmol) of copper (II) chloride, and 14 mg (0.08 mmol) of palladium chloride. After replacing the gas environment in the system with carbon monoxide, a solution obtained by dissolving 20 g (76.7 mmol) of CYPDM in 66 g of chloroform was added dropwise over 6 hours, and reacted at room temperature for 3 hours. Next, after replacing the gas environment in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 300 g of chloroform was added. After concentrating under reduced pressure, the solvent was distilled off, and 300 g of chloroform was added. The insoluble matter was removed from the obtained tea green suspension by filtration. The obtained solution was washed three times with 240 g of a saturated sodium bicarbonate aqueous solution and three times with 240 g of purified water, and then 4 g of anhydrous magnesium sulfate and 2 g of activated carbon were added to the organic layer and stirred. The solution was filtered and concentrated under reduced pressure to obtain 26.7 g of a light brown solid. Next, purification by silica gel chromatography (developing solvent; hexane: ethyl acetate = 15: 1 (volume ratio)) was performed, and then recrystallization (solvent ratio; toluene / heptane = 2.5: 1 (volume ratio) was performed. )) Refined to obtain 22.4 g of white solid 1,2,3,4-tetrahydro-1,4-methyl bridge naphthalene-2,3,6,7-tetracarboxylic acid (BNME) (HPLC Analytical analysis revealed a purity of 94.8 pa% and a yield of 67.5%).

The physical properties of BNME are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.89 (d, J = 10 Hz, 1H), 2.54 (d, J = 10 Hz, 1H), 2.74 (d, J = 2.0 Hz, 2H), 3.67 ( t, J = 2.0Hz, 2H), 3.70 (s, 6H), 3.89 (s, 6H), 7.57 (s, 2H) CI-MS (m / z); 377 (M + 1)

In a reaction container with a capacity of 200 mL, 20 g (50.4 mmol) of BNME, 60 g of formic acid, and 194.2 mg (1.02 mmol) of p-toluenesulfonic acid monohydrate were added, and reacted at an internal temperature of 95 ° C to 99 ° C for 57 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 42 g of toluene was added to the concentrate. This operation was repeated 7 times, and formic acid was almost completely distilled off. The obtained suspension was filtered, and the obtained solid was washed with 21 g of toluene, and then dried under vacuum at 80 ° C. to obtain 16.1 g of a milky white solid. Thereafter, recrystallization using acetic anhydride was performed, and recrystallization using N, N'-dimethylacetamide was performed to obtain 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-formaldehyde. Bridgenaphtho [2,3-c: 6,7-c '] difuran-1,3,6,8-tetraone (BNDA) 8.39 g (purity 98.8% by ¹ H-NMR analysis, Yield: 57.9%).

Furthermore, 15 g of the obtained BNDA was used for refining at a sublimation condition of 220 to 230 ° C./5 Pa to obtain 11.6 g of BNDA as a white solid (100% purity by ¹ H-NMR analysis and 76.4% recovery).

The physical properties of BNDA are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 1.79 (d, J = 15 Hz, 1H), 1.93 (d, J = 15 Hz, 1H), 3.21 (s, 2H), 4.05 (s, 2H ), 8.07 (s, 2H) CI-MS (m / z); 285 (M + 1)

[Example 1] In a reaction vessel substituted with nitrogen, 0.60 g (2.6 mmol) of DABAN was charged, and NMP 6.29 g was added, and the amount was based on the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component). ) To an amount of 20% by mass, and stirred at room temperature for 1 hour. To this solution was slowly added 1.12 g (2.6 mmol) of TNDA. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated to room temperature to 440 ° C directly on the glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to perform thermal hydrazone imine. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 2] In a reaction vessel substituted with nitrogen, 1.00 g (4.4 mmol) of DABAN, 0.07 g (0.6 mmol) of PPD, and 0.46 g (1.3 mmol) of BAPB were added, and 11.54 g of NMP was added. This amount is an amount such that the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) becomes 25% by mass, and the mixture is stirred at room temperature for 1 hour. To this solution was slowly added 2.32 g (6.3 mmol) of TNDA. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

A polyimide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 460 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to perform thermal imidization. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Comparative Example 1] In a reaction container substituted with nitrogen, 1.00 g (2.7 mmol) of BAPB was charged, and NMP 6.00 g was added. This amount is based on the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component). ) To an amount of 25% by mass, and stirred at room temperature for 1 hour. To this solution was slowly added 1.00 g (2.7 mmol) of TNDA. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 430 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Comparative Example 2] A reaction vessel substituted with nitrogen was charged with 0.70 g (3.5 mmol) of 4,4'-ODA, and 7.95 g of DMAc was added. This amount is based on the total mass of the feed monomer (diamine component and The sum of the carboxylic acid components) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 1.29 g (3.5 mmol) of TNDA. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 430 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 3] 0.23 g (1.0 mmol) of DABAN was charged into a reaction container substituted with nitrogen, and 2.70 g of NMP was added. This amount is based on the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component). ) To an amount of 16% by mass, and stirred at room temperature for 1 hour. To this solution, 0.29 g (1.0 mmol) of BNDA obtained in Example S-3 was slowly added. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 320 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 4] 0.40 g (3.7 mmol) of PPD was charged into a nitrogen-substituted reaction container, and NMP 5.81 g was added. This amount is based on the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component). ) To an amount of 20% by mass, and stirred at room temperature for 1 hour. To this solution was slowly added 1.05 g (3.7 mmol) of BNDA obtained in Example S-3. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

A polyimide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated from room temperature to 350 ° C. directly on a glass substrate under a nitrogen atmosphere (oxygen concentration below 200 ppm), and then subjected to thermal fluoridation. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 5] A reaction vessel substituted with nitrogen was charged with TFMB 1.52 g (4.7 mmol), and NMP 11.41 g was added. This amount was based on the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component). ) To an amount of 20% by mass, and stirred at room temperature for 1 hour. To this solution was slowly added 1.35 g (4.7 mmol) of BNDA obtained in Example S-3. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 320 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 6] In a reaction vessel substituted with nitrogen, 0.40 g (1.8 mmol) of DABAN, 0.70 g (2.2 mmol) of TFMB, and 0.16 g (0.4 mmol) of BAPB were added, and 10.00 g of NMP was added. This amount is an amount such that the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) becomes 20% by mass, and the mixture is stirred at room temperature for 1 hour. To this solution was slowly added 1.24 g (4.4 mmol) of BNDA obtained in Example S-3. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

A polyimide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated from room temperature to 350 ° C. directly on a glass substrate under a nitrogen atmosphere (oxygen concentration below 200 ppm), and then subjected to thermal fluoridation. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 7] 0.39 g (3.5 mmol) of tra-DACH was charged into a reaction container substituted with nitrogen, and 11.14 g of NMP was added. This amount is based on the total mass of the feed monomer (diamine component and carboxylic acid component The total amount was 11% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 0.98 g (3.5 mmol) of BNDA obtained in Example S-3. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 320 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Comparative Example 3] In a reaction container substituted with nitrogen, 4,0'-ODA 0.60 g (3.0 mmol) was added, and 13.06 g of NMP was added. This amount is based on the total mass of the feed monomer (diamine component and The sum of the carboxylic acid components) was 10% by mass, and the mixture was stirred at room temperature for 1 hour. Here, 0.85 g (3.0 mmol) of BNDA obtained in Example S-3 was slowly added. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 320 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then thermally fluorinated. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 8] In a reaction container substituted with nitrogen, 4,0'-ODA 0.70 g (3.5 mmol) was added, and 25.57 g of NMP was added. This amount was based on the total mass of the feed monomer (diamine component and The sum of the carboxylic acid components) was 7% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 1.22 g (3.5 mmol) of DMADA obtained in Example S-1. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

A polyimide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated from room temperature to 350 ° C. directly on a glass substrate under a nitrogen atmosphere (oxygen concentration below 200 ppm), and then subjected to thermal fluoridation. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

[Example 9] TPE-R1.20g (4.1 millimolar) was charged into a reaction container substituted with nitrogen, and NMP11.39g was added. This amount is based on the total mass of the feed monomer (diamine component and carboxylic acid component). The total amount was 25% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 1.32 g (4.1 mmol) of EMDAxx obtained in Example S-2-2. Stir at room temperature for 48 hours to obtain a homogeneous and viscous polyimide precursor solution.

The polyfluorene imide precursor solution filtered through a PTFE filter membrane was coated on a glass substrate, and heated to 450 ° C from room temperature directly on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to perform thermal fluorination. A colorless and transparent polyfluorene imide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

Table 2 shows the results of measuring the characteristics of the polyfluoreneimide film.

【Table 2】

From the results shown in Table 2-1, it can be seen that when using TNDA as the tetracarboxylic acid component, compared to using only diamine (4,4'-ODA, BAPB) having an ether bond (-O-) as the diamine component In the case of using a diamine (DABAN, PPD) having a structure of the aforementioned chemical formula (B-1) having no ether bond (-O-), sufficient transparency and mechanical properties can be maintained, and the obtained polyimide High heat resistance and low coefficient of linear thermal expansion (Examples 1, 2 and Comparative Examples 1, 2). In the case of using BNDA as the tetracarboxylic acid component, compared with the case where only a diamine (4,4'-ODA) having an ether bond (-O-) is used as a diamine component, a non-ether bond (-O-) is used. When the diamine (DABAN, PPD, TFMB) of the structure of the aforementioned chemical formula (B-1) and the diamine (tra-DACH) of the structure of the aforementioned chemical formula (B-2) are used, sufficient transparency and mechanical properties will be maintained. And the linear thermal expansion coefficient of the obtained polyimide is extremely low, and the heat resistance is also equal to or higher (Examples 3 to 7 and Comparative Example 3).

In addition, it can be seen that the combined diamine components are the same. When DMADA is used as the tetracarboxylic acid component, the linear thermal expansion coefficient of the polyfluorene imine obtained is lower than that when BNDA is used (Example 8 and Comparative Example 3).

When EMDA is used as the tetracarboxylic acid component, polyimide having a low linear thermal expansion coefficient, high heat resistance, and sufficient characteristics can be obtained (Example 9). [Industrial availability]

According to the present invention, polyimide having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, a precursor thereof, and a novel tetracarboxylic acid used in the production thereof can be provided. anhydride. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency and low coefficient of linear thermal expansion, are easy to form fine circuits, and have solvent resistance, and are particularly suitable for forming Substrates for display applications, etc.

no

Claims (21)

A polyimide precursor comprising at least one of the repeating units represented by the following chemical formula (1-1), and the total content of the repeating units represented by the chemical formula (1-1) is 50 with respect to the total repeating units. More than% Mohr; [化 1]

In the formula, A ₁₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₁₁ is a divalent group represented by the following chemical formula (B-1), or A divalent group represented by the following chemical formula (B-2), X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl silyl group having 3 to 9 carbon atoms;

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a member selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the groups, Q ₁ and Q ₂ each independently represent a member selected from the group consisting of a group represented by a direct bond, or a formula: -NHCO-, -CONH-, -COO-, -OCO- 1 species; [chemical 5]

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A polyfluorene imide precursor, comprising: at least one of the repeating units represented by the following chemical formula (1-2);

In the formula, A ₁₂ is a tetravalent group represented by the following chemical formula (A-3) or a tetravalent group represented by the following chemical formula (A-4), B ₁₂ is a divalent group having an aromatic ring or an alicyclic structure, and X ₃ and X ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms;

In the formula, R ₅ and R ₆ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. For example, the polyimide precursor of item 2 of the patent application range, wherein the total content of the repeating units represented by the chemical formula (1-2) is 50 mol% or more relative to the total repeating units. A polyimide, characterized in that it comprises at least one of the repeating units represented by the following chemical formula (2-1), and the total content of the repeating units represented by the chemical formula (2-1) is 50 mol% relative to all the repeating units Above; [化 9]

In the formula, A ₂₁ is a tetravalent group represented by the following chemical formula (A-1) or a tetravalent group represented by the following chemical formula (A-2), and B ₂₁ is a divalent group represented by the following chemical formula (B-1), or A divalent group represented by the following chemical formula (B-2);

In the formula, R ₁ , R ₂ , and R ₃ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3; Y ₁ , Y ₂ , and Y ₃ each independently represent a member selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. One of the groups, Q ₁ and Q ₂ each independently represent a member selected from the group consisting of a group represented by a direct bond, or a formula: -NHCO-, -CONH-, -COO-, -OCO- 1 species;

In the formula, Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A polyimide characterized by comprising at least one of the repeating units represented by the following chemical formula (2-2); [Chem. 14]

In the formula, A ₂₂ is a tetravalent group represented by the following chemical formula (A-3) or a tetravalent group represented by the following chemical formula (A-4), and B ₂₂ is a divalent group having an aromatic ring or an alicyclic structure; 15]

In the formula, R ₅ and R ₆ are each independently -CH _2- , -CH ₂ CH _2- , or -CH = CH-; [Chem. 16]

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. For example, the polyimide of the scope of the patent application No. 5 wherein the total content of the repeating unit represented by the chemical formula (2-2) is 50 mol% or more relative to the total repeating unit. A polyimide is obtained from a polyimide precursor as described in any one of claims 1 to 3 of the patent application scope. A membrane, which is obtained from a polyimide precursor as described in any one of claims 1 to 3, or a polyimide as described in any of claims 4 to 6, Based on amines. A varnish comprising a polyimide precursor as described in any one of claims 1 to 3, or a polyimide as described in any one of claims 4 to 6. A polyimide film using a polyimide precursor containing any one of claims 1 to 3 of the patent application scope, or a polyimide containing any one of claims 4 to 6 of the patent application scope The varnish is obtained. A substrate for a display, a touch panel, or a solar cell, characterized in that it contains polyimide obtained from a polyimide precursor as described in any one of claims 1 to 3, or Such as the application of any of the scope of patents 4 to 6 polyimide. A tetracarboxylic dianhydride represented by the following chemical formula (M-1);

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —. A tetraester compound represented by the following chemical formula (M-2);

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms. . A tetraester compound represented by the following chemical formula (M-3);

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms. . A method for producing tetracarboxylic dianhydride, comprising the following steps: (A) reacting an olefin compound represented by the following chemical formula (MA-1) with an aliphatic sulfonium chloride or an aromatic sulfonium chloride in the presence of a base; And an olefin compound represented by the following chemical formula (MA-2) was obtained;

In the formula, R ₅ ′ and R ₆ ′ are each independently —CH ₂ — or —CH ₂ CH ₂ —;

In the formula, R ₅ ′ and R ₆ ′ have the same meanings as described above, and R is an alkyl group or an aryl group which may have a substituent; (B) The olefin compound represented by the chemical formula (MA-2) is reacted with In the presence of the compound, the alcohol compound is reacted with carbon monoxide to obtain a tetraester compound represented by the following chemical formula (MA-3);

In the formula, R ₅ ′, R ₆ ′, and R have the same meanings as above, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently an alkyl group having 1 to 10 carbon atoms; (C) From the chemical formula (MA- 3) A tetraester compound represented by the following formula: A tetraester compound represented by the following chemical formula (M-3) is obtained;

In the formula, R ₅ ′, R ₆ ′, R ₁₁ , R ₁₂ , R ₁₃ , R _{14 have} the same meanings as above; (D) The oxidation reaction of the tetraester compound represented by the chemical formula (M-3) gives the following chemical formula ( Tetraester compound represented by M-2); [Chem. 24]

In the formula, R ₅ ′, R ₆ ′, R ₁₁ , R ₁₂ , R ₁₃ , R _{14 have} the same meanings as above; (E) The tetraester compound represented by the chemical formula (M-2) is present in the presence of an acid catalyst in Reaction in an organic solvent to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-1);

In the formula, R ₅ ′ and R ₆ ′ have the same meanings as described above. A tetracarboxylic dianhydride represented by the following chemical formula (M-4);

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-. A tetraester compound represented by the following chemical formula (M-5);

In the formula, R ₇ is -CH ₂ CH _2- , or -CH = CH-, and R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbon atoms. A dihalodicarboxylic anhydride represented by the following chemical formula (M-6);

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I. A dicarboxylic anhydride represented by the following chemical formula (M-7);

A method for producing a tetracarboxylic dianhydride, comprising the following steps: (A) reacting a dicarboxylic anhydride represented by the following chemical formula (MB) with 1,3-butadiene to obtain the following chemical formula (M-7) Dicarboxylic anhydride

[Chemical 31]

(B) reacting a dicarboxylic anhydride represented by the chemical formula (M-7) with a dihalogenating agent to obtain a dihalodicarboxylic anhydride represented by the following chemical formula (M-6);

In the formula, X ₁₁ and X ₁₂ each independently represent any one of -F, -Cl, -Br, or -I; (C) the dihalodicarboxylic anhydride represented by the chemical formula (M-6) and Maleic anhydride is reacted to obtain tetracarboxylic dianhydride represented by the following chemical formula (M-4-1);

(D) reacting a tetracarboxylic dianhydride represented by the chemical formula (M-4-1) with an alcohol compound in the presence of an acid to obtain a tetraester compound represented by the following chemical formula (M-5-1);

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently an alkyl group having 1 to 10 carbon atoms; (E) The tetraester compound represented by the chemical formula (M-5-1) is present in a metal catalyst And reacting with hydrogen to obtain a tetraester compound represented by the following chemical formula (M-5-2);

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R _{24 have} the same meanings as above; (F) reacting the tetraester compound represented by the chemical formula (M-5-2) in an organic solvent in the presence of an acid catalyst to obtain Tetracarboxylic dianhydride represented by the following chemical formula (M-4-2);

. A method for producing a tetracarboxylic dianhydride, comprising the following steps: (A) reacting a diene compound represented by the following chemical formula (MC-1) with an acetylene compound represented by the following chemical formula (MC-2) to obtain the following chemical formula A diester compound represented by (MC-3);

In the formula, R ₄ is -CH _2- , -CH ₂ CH _2- , or -CH = CH-;

In the formula, R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group;

In the formula, R ₄ , R ₃₁ and R _{32 have} the same meanings as above; (B) The oxidation reaction of the diester compound represented by the chemical formula (MC-3) is used to obtain the diester compound represented by the following chemical formula (MC-4); [Chemical 40]

In the formula, R ₄ , R ₃₁ and R _{32 have} the same meanings as above; (C) The diester compound represented by the chemical formula (MC-4) is reacted with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain the following Tetraester compound represented by Chemical Formula (MC-5);

In the formula, R ₄ , R ₃₁ , and R _{32 have} the same meanings as above, and R ₃₃ and R ₃₄ are each independently an alkyl group having 1 to 10 carbon atoms; (D) a tetraester compound represented by the chemical formula (MC-5) Reaction in an organic solvent in the presence of an acid catalyst to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-9);

In the formula, R _{4 has} the same meaning as described above.