Polyimide compounds

Abstract

The present invention relates to a polyimide compound represented by formula (I) (in the formula, each symbol has the same meaning as disclosed in the specification).

Description

[Technical Field]

[0001] This disclosure relates to polyimide compounds, their raw material monomers, and intermediates. [Background technology]

[0002] Polyimide possesses excellent properties such as heat resistance, mechanical properties, and insulating properties. Therefore, polyimide is widely used in various applications, such as automotive components, aircraft components, and electrical and electronic components (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-203981 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Because polyimides are used in a wide range of applications, there is a demand for polyimides with various structures. [Means for solving the problem]

[0005] This disclosure includes the following aspects: [1] The following formula (I): [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6A group selected from an alkoxy group and a halogen atom, A 1 is a linear or branched C 4-16 perfluoroalkylene group, A 2 is an aliphatic or aromatic bisimide-N’,N-diyl, n1 is an arbitrary integer.] The polyimide compound represented by [2] Ar 1 and Ar 2 are phenylenes substituted by one or more substituents selected from a C 1-6 alkyl group, a C 1-6 alkoxy group, and a halogen atom, the polyimide compound according to [1] above. [3] The formula (I) is the following formula (Ia’):

Chemical formula

[10] Formula (II) below: [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 3 It is a divalent organic group, n1 is any integer. A compound represented by the formula.

[11] The following formula (III): [ka] [In formula: Ar 3 This is an unsubstituted phenylene group or an indolylene group, A 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, n2 is an arbitrary integer. A polyimide compound represented by

[12] The formula (III) is the following formula (IIIa):

Chemical formula

[11] , represented by

[13] R 31 、and R 32 are each independently a C 1-6 alkyl group, a C 1-6 alkoxy group, or a halogen atom, R<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​15 , R 16 , R 17 , and R 18 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, However, R 11 , R 12 , R 13 , and R 14 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 15 , R 16 , R 17 , and R 18 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 At least one of them is not a fluorine atom, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. A diamine compound represented by [the specified symbol].

[16] R 11 , R 12 , R 15 , and R 16 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 13 , R 14 , R 17 , and R 18 is a hydrogen atom The diamine compounds described above

[15] .

[17] R 11 , R 12 , R 15 , and R 16 C1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 13 , R 14 , R 17 , and R 18 is a hydrogen atom The diamine compounds described in

[15] or

[16] above.

[18] The following equation (VI): [ka] [In formula: R 31 , R 32 , R 33 , and R 34 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, A 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. A compound represented by the formula.

[19] R 31 , and R 32 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 33 , and R 34 is a hydrogen atom The compounds described above

[18] .

[20] R 31 , and R 32 C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 33 , and R 34 is a hydrogen atom The compounds described in

[18] or

[19] above.

[21] Equation (IV) above: [ka] [In formula: Ar1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. A method for producing a diamine compound represented by the following: The following equation (VII): H-Ar 4 -NH2 [In the formula, Ar 4 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 It is a group selected from alkoxy groups and halogen atoms. A compound represented by the following formula (VIII): IA 1 -I [In the formula, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. A method for producing a compound represented by under light irradiation. [Effects of the Invention]

[0006] The present invention can provide polyimides having various structures. [Modes for carrying out the invention]

[0007] This disclosure is based on the following formula (I): [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 2 It is an aliphatic or aromatic bisimide-N',N-diyl, n1 is any integer. The present invention provides a polyimide compound represented by the following:

[0008] In one embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0009] In another embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 The indolylene group may be substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0010] In one embodiment, Ar 2 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0011] In another embodiment, Ar 2 C 1-6Alkyl alkyl group, C 1-6 The indolylene group may be substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0012] In one embodiment, Ar 1 and Ar 2 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0013] In one embodiment, Ar 1 and Ar 2 C 1-6 Alkyl alkyl group, C 1-6 The indolylene group may be substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0014] In one embodiment, the indorylene group is unsubstituted.

[0015] In another embodiment, the indolylene group is C 1-6 Alkyl alkyl group, C 1-6 It is substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0016] The polyimide compounds of this disclosure have improved adhesion to metal surfaces due to the presence of an indole ring.

[0017] In the polyimide compounds disclosed herein, for example, Ar is present on the aromatic ring. 1 and Ar 2 The benzene ring and indole ring may have one or more substituents. The polyimide compounds of this disclosure may have various properties due to having such substituents.

[0018] C as a substituent on the phenylene group or indolylene group mentioned above. 1-6 The alkyl group may be linear or branched, preferably C 1-3It is an alkyl group, more preferably a methyl group or an ethyl group.

[0019] The polyimide compound of the present disclosure may have excellent flexibility and / or solvent solubility by having a C 1-6 alkyl group as the above substituent.

[0020] The C 1-6 alkoxy group as a substituent of the above phenylene group or indolylene group may be linear or branched, preferably a C 1-3 alkoxy group, more preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group.

[0021] The polyimide compound of the present disclosure may have solvent solubility and / or excellent flexibility by having a C 1-6 alkoxy group as the above substituent.

[0022] The halogen atom as a substituent of the above phenylene group or indolylene group is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom.

[0023] In one aspect, the halogen atom is a fluorine atom. The polyimide compound of the present disclosure may have excellent transparency, low dielectric constant and flame retardancy by having a fluorine atom as the above substituent. <00,009,08> In another aspect, the halogen atom is a chlorine atom. The polyimide compound of the present disclosure may have high flame retardancy by having a chlorine atom as the above substituent.

[0025] In a preferred embodiment, the number of substituents of the above phenylene group or indolylene group may be 2 or more, for example, 2 to 4. Also, when there are a plurality of such substituents, Ar 1 or Ar 2 The substituents in may be the same or different, but are preferably the same.

[0026] In a preferred embodiment, the substituents on the phenylene group or indolylene group are A 2 It bonds to an atom adjacent to the atom it is bonding to. For example, Ar 1 Or Ar 2 If A is phenylene, 2 C is located at the ortho position relative to the atom to which it is bonded. 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or halogen atom is located there.

[0027] In a more preferred embodiment, the substituents on the phenylene group or indolylene group are A 2 On two atoms adjacent to the atom to which it is bonded, the same C 1-6 The polyimide compounds of this disclosure have the same C 1-6 The presence of an alkyl group, preferably a methyl or ethyl group, can raise the glass transition temperature and improve the char formation rate.

[0028] A above 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. 4-16 The perfluoroalkylene group is preferably C 4-12 Perfluoroalkylene group, more preferably C 4-10 A perfluoroalkylene group, more preferably C 4-8 It is a perfluoroalkylene group. In one embodiment, the above C 4-16 The perfluoroalkylene group is linear. In another embodiment, the above C 4-16 The perfluoroalkylene group is a branched chain. In a preferred embodiment, the above C 4-16 The perfluoroalkylene group is a straight-chain carbon 4-8 It is a perfluoroalkylene group.

[0029] The polyimide compounds disclosed herein are A 1 as C 4-16 The inclusion of perfluoroalkylene groups may improve transparency, flexibility, low dielectric properties, and / or solvent solubility.

[0030] A above 2 It is an aliphatic or aromatic bisimide-N',N-diyl. That is, the structure is as follows: [ka] It is a base that has two of them.

[0031] A above 2 It typically originates from tetracarboxylic acid, a raw material for polyimides represented by formula (I).

[0032] The above n1 is any integer, preferably 2 to 500, more preferably 2 to 100, even more preferably 5 to 100, and particularly preferably 5 to 50.

[0033] In a preferred embodiment, formula (I) above is the following formula (Ia): [ka] [In formula: R 10 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, q1 is an integer between 1 and 4, preferably between 2 and 4, and more preferably 2. A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 2 It is an aliphatic or aromatic bisimide-N',N-diyl, n1 is any integer. That is the case.

[0034] In a preferred embodiment, formula (I) above is the following formula (Ia'): [ka] [In formula: R 11 , R 12 , R 15 , and R16 is, independently of each other, C 1-6 alkyl group, C 1-6 alkoxy group, or halogen atom, R 13 R 14 R 17 and R 18 is a hydrogen atom, A 1 is a straight-chain or branched-chain C 4-16 perfluoroalkylene group, A 2 is an aliphatic or aromatic bisimide-N’,N-diyl, n1 is an arbitrary integer.] is.

[0035] That is, Ar in the above formula (I) 1 is the following formula:

Chemical formula

[0038] In a more preferred embodiment, the above R 11 and R 12 C 1-6 Alkyl alkyl group, C 1-6 The above R is an alkoxy group or a halogen atom. 15 and R 16 C 1-6 Alkyl alkyl group, C 1-6 The above R is an alkoxy group or a halogen atom. 13 , R 14 , R 17 , and R 18 This is a hydrogen atom.

[0039] In a preferred embodiment, formula (I) above is the following formula (Ib): [ka] [In formula: R 19 In each occurrence, C is independent. 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 20 In each occurrence, C is independent. 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, p1 is an integer between 0 and 5. p2 is an integer between 0 and 5. A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 2 It is an aliphatic or aromatic bisimide-N',N-diyl, n1 is any integer. That is the case. Furthermore, the above R 19 and R 20This substituent is bonded to the indole ring and may be bonded at any position on the indole ring.

[0040] In a preferred embodiment, A 1 It is bonded to the 2nd or 3rd position of the indole ring. In one embodiment, A 1 It bonds to the 3-position of the indole ring. In another embodiment, A 1 It is bonded to the 2nd position of one indole ring and to the 3rd position of the other indole ring.

[0041] In a preferred embodiment, A 2 The molecule is bonded to the 4th to 7th position of the indole ring, preferably at the 5th or 6th position, and more preferably at the 5th position.

[0042] In one embodiment, p1 and p2 are 0.

[0043] In another embodiment, p1 and p2 are integers from 1 to 5, preferably integers from 2 to 4. For example, it is 2.

[0044] In one embodiment, the above formula (I) is the following formula (Ic): [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 3 These are single bonds or divalent organic groups, n1 is any integer. That is the case.

[0045] That is, A in equation (I) above 2 However, the following formula: [ka] It is a base represented by .

[0046] In a preferred embodiment, A 3 C may be substituted with single, linear, or branched fluorine atoms. 1-16 Alkylene group, oxygen atom, -CO-, -C≡C-, -SO2-, [ka] That is the case.

[0047] A above 3 C may be substituted with linear or branched fluorine atoms in the given C 1-16 C of the alkylene group 1-16 The alkylene group is preferably C 1-10 Alkylene group, more preferably C 1-6 It may be an alkylene group.

[0048] In one aspect, such C 1-16 The alkylene group is substituted with one or more fluorine atoms. In one embodiment, such C 1-16 The alkylene group may be a so-called perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms.

[0049] In a preferred embodiment, A 2 is a group selected from the following groups. [ka]

[0050] [ka]

[0051] In a preferred embodiment, formula (I) above is the following formula (Id): [ka] [In formula: R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, However, R 11 , R 12 , R 13 , and R 14 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 15 , R 16 , R 17 , and R 18 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 3 These are single bonds or divalent organic groups, n1 is any integer. It is represented as follows.

[0052] This disclosure also provides intermediates in the production of the above-mentioned polyimide compounds.

[0053] The above intermediate is given by the following formula (II): [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, A 3 It is a divalent organic group, n1 is any integer. It is a compound represented by [formula].

[0054] In a preferred embodiment, formula (II) above is the following formula (IIa): [ka] [In the formula, Ar 1 Ar 2 , A 1 , A 3 And n1 have the same meaning as described in formula (II) above. It is a compound represented by [formula].

[0055] The polyimide compound represented by the above formula (I) is (1) The following formula (IV): [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It can be obtained by reacting a diamine compound represented by with a tetracarboxylic acid or its anhydride.

[0056] In one embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 2 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0057] In one embodiment, the compound represented by formula (IV) above is given by the following formula (IVa): [ka] [In formula: R 10 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, q1 is an integer between 1 and 4, preferably between 2 and 4, and more preferably 2. A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It is a diamine compound represented by [formula].

[0058] In one embodiment, the compound represented by formula (IV) above is given by the following formula (IVb): [ka] [In formula: R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, However, R 11 , R 12 , R 13 , and R 14 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 15 , R 16 , R 17 , and R 18 At least one of them is C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 At least one of them is not a fluorine atom, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It is a diamine compound represented by [formula].

[0059] In another embodiment, the compound represented by formula (IV) above is given by the following formula (IVc): [ka] [In formula: R 11 , R 12 , R 15 , R16 , R 13 , R 14 , R 17 , R 18 , and A 1 This is equivalent to the description in formula (IVb) above. It is a diamine compound represented by [formula].

[0060] In a preferred embodiment, R 11 , R 12 , R 15 , and R 16 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 13 , R 14 , R 17 , and R 18 This is a hydrogen atom.

[0061] In a more preferred embodiment, R 11 , R 12 , R 15 , and R 16 C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 13 , R 14 , R 17 , and R 18 This is a hydrogen atom.

[0062] In another embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 An indolylene group which may be substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 2 C 1-6 Alkyl alkyl group, C 1-6 The indolylene group may be substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0063] In another embodiment, the compound represented by formula (IV) above is given by the following formula (IVd): [ka] [In formula: R 19 In each occurrence, C is independent. 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, R 20 In each occurrence, C is independent. 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, p1 is an integer between 0 and 5. p2 is an integer between 0 and 5. A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It is a diamine compound represented by [formula].

[0064] In one embodiment, p1 and p2 are 0.

[0065] In another embodiment, p1 and p2 are integers from 1 to 5, preferably integers from 2 to 4. For example, it is 2.

[0066] In a preferred embodiment, A 1 C 4-12 Perfluoroalkylene group, more preferably C 4-10 A perfluoroalkylene group, more preferably C 4-8 It is a perfluoroalkylene group. In one embodiment, the above C 4-16 The perfluoroalkylene group is linear. In another embodiment, the above C 4-16 The perfluoroalkylene group is a branched chain.

[0067] Equation (IV) above: [ka] [In formula: Ar 1 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. Ar 2 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 A group selected from alkoxy groups and halogen atoms, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. The diamine compounds represented by the following are The following equation (VII): H-Ar 4 -NH2 [In the formula, Ar 4 This is a phenylene group substituted with one or more substituents, or an indolylene group which may be substituted with one or more substituents. The substituent is C 1-6 Alkyl alkyl group, C 1-6 It is a group selected from alkoxy groups and halogen atoms. A compound represented by the following formula (VIII): IA 1 -I [In the formula, A 1 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It can be obtained by reacting the compound represented by under light irradiation.

[0068] The above Ar 4 In equation (IV), Ar 1 and Ar 2 It corresponds to.

[0069] In the above reaction, one compound represented by formula (VII) reacts with two compounds represented by formula (VIII). These two compounds represented by formula (VIII) may have the same structure or different structures. Preferably, there is only one compound represented by formula (VIII). That is, one compound represented by formula (VII) reacts with two compounds represented by formula (VIII) that have the same structure.

[0070] In one embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 2 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 4 C 1-6 Alkyl alkyl group, C 1-6 A phenylene group substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0071] In another embodiment, Ar 1 C 1-6 Alkyl alkyl group, C 1-6 An indolylene group which may be substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 2 C 1-6 Alkyl alkyl group, C 1-6 An indolylene group which may be substituted with one or more substituents selected from alkoxy groups and halogen atoms, Ar 4 C 1-6 Alkyl alkyl group, C 1-6 The indolylene group may be substituted with one or more substituents selected from alkoxy groups and halogen atoms.

[0072] The above-mentioned light irradiation is preferably ultraviolet irradiation, and is carried out by irradiating with light of a wavelength of 300-400 nm, for example, 350-380 nm.

[0073] The light source used for such light irradiation is not particularly limited, but examples include LEDs, mercury lamps, xenon lamps, UV lamps, halogen lamps, etc., and LEDs are preferably used.

[0074] The above reaction can preferably be carried out using a basic compound, a catalyst, a one-electron reducing agent, or a radical generating agent.

[0075] Examples of the basic compounds mentioned above include inorganic bases such as Cs2CO3, K2CO3, Na2CO3, Li2CO3, CsF, CsHCO3, KHCO3, NaHCO3, and LiHCO3; amine compounds such as triethylamine, tributylamine, diisopropylethylamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetraethylenediamine, pyrrolidine, pyridine, colidine, ammonia, dimethylamine, and DBU; tributylphosphine, triphenylphosphine, triarylphosphines, and disubstituted phosphines, with Cs2CO3 being preferred.

[0076] Examples of the catalysts mentioned above include transition metal complexes, organic dye compounds, and enamine compounds.

[0077] Examples of central metal species found in the above transition metal complexes include cobalt, ruthenium, rhodium, rhenium, iridium, zinc, nickel, palladium, osmium, and platinum.

[0078] Examples of the above organic pigment compounds include rose bengal, erythrosine, eosin (e.g., eosin B, eosin Y), acriflavin, lipoflavin, thionine, phenoxazine, and phenothiazine.

[0079] The above enamine compound [ka] The structure is represented by aldehydes. [ka] [In the formula, R 1 R is a phenyl group or a benzyl group, 2 This is a hydrogen atom, a methyl group, or a phenyl group. and pyrrolidines [ka] [In the formula, R 3 This is a hydrogen atom or a bis(3,4-dimethoxyphenyl)methoxymethyl group. This is a chemical species generated by the reaction. A pre-synthesized enamine compound may be added, or the aldehyde and pyrroles may be added directly to generate a catalyst in the reaction system.

[0080] Examples of the above-mentioned aldehydes include 3-phenyl-2-methylpropanal, 2-phenylpropanal, diphenylacetaldehyde, and phenylacetaldehyde.

[0081] Examples of the above-mentioned pyrrolidines include pyrrolidine and (S)-2-[3,4-bis(dimethoxyphenyl)methoxymethyl]pyrrolidine.

[0082] Examples of the above-mentioned one-electron reducing agent include sodium thiosulfate, lithium dithionite, sodium dithionite, potassium dithionite, cesium dithionite, copper(I) iodide, copper(I) bromide, copper(I) chloride, triethylamine, tributylamine, tetrabutylammonium iodide, tetrabutylphosphonium iodide, ascorbic acid, ascorbate, zinc powder, indium powder, magnesium powder, etc. Preferably, it is sodium thiosulfate, sodium dithionite, copper(I) iodide, or copper(I) bromide, and particularly preferably sodium thiosulfate or sodium dithionite.

[0083] Examples of the radical generating agents mentioned above include organic peroxides, inorganic peroxides, and organic azo compounds, with organic peroxides being preferred. While not limited to the following, examples of organic peroxides include benzoyl peroxide, inorganic peroxides include potassium persulfite, and organic azo compounds include azobisisobutyronitrile (AIBN).

[0084] The above reaction is preferably carried out in a solvent. Such solvents are not particularly limited, but include, for example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dichloropentafluoropropane (HCFC-225), perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F 13 CH2CH3 (e.g., AsahiClean® AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeolora® H manufactured by Nippon Zeon Co., Ltd.); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Limited), perfluoro Examples include alkyl perfluoroalkyl ethers such as chlorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.).

[0085] The reaction temperature in the above reaction is preferably 0 to 60°C, more preferably 10 to 40°C, and may be, for example, room temperature.

[0086] The reaction time in the above reaction may be, for example, 1 to 72 hours, preferably 12 to 48 hours.

[0087] The above-mentioned tetracarboxylic acid or its anhydride is not particularly limited as long as it can react with the above-mentioned diamine compound to form a polyimide compound, and may be an aliphatic or aromatic tetracarboxylic acid or its anhydride.

[0088] In a preferred embodiment, the tetracarboxylic acid or its anhydride is a tetracarboxylic anhydride.

[0089] Examples of the above-mentioned aliphatic tetracarboxylic anhydrides include the following compounds. [ka]

[0090] Examples of the above-mentioned aromatic tetracarboxylic anhydrides include the following compounds. [ka]

[0091] This disclosure also relates to the following formula (III): [ka] [In formula: Ar 3 This is an unsubstituted phenylene group or an indolylene group, A 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, n² is any integer. The present invention provides a polyimide compound represented by the following:

[0092] The polyimide compound represented by the above formula (III) consists of a phthalic acid-derived portion and an aromatic ring portion (Ar 3 Because these molecules are arranged alternately, polarization is generated in the direction of the molecular main chain, which can result in high solubility.

[0093] In one embodiment, the above Ar 3 This is a phenylene group that may be substituted.

[0094] In another embodiment, the above Ar 3 This is an indrolene group that may be substituted.

[0095] The above Ar 3 A substituent that may be substituted on the phenylene group or indolylene group in is, for example, C 1-6 Alkyl alkyl group, C 1-6 Examples include alkoxy groups and halogen atoms.

[0096] C above 1-6 The alkyl group may be linear or branched, preferably C 1-3 An alkyl group, more preferably a methyl group.

[0097] C above 1-6 The alkoxy group may be linear or branched, preferably C 1-3 The group is an alkoxy group, more preferably a methoxy group or a methyl group, and particularly preferably a methoxy group.

[0098] The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

[0099] A above 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. 4-16 The perfluoroalkylene group is preferably C 4-12 Perfluoroalkylene group, more preferably C 4-10A perfluoroalkylene group, more preferably C 4-8 It is a perfluoroalkylene group. In one embodiment, the above C 4-16 The perfluoroalkylene group is linear. In another embodiment, the above C 4-16 The perfluoroalkylene group is a branched chain.

[0100] The above n2 is any integer, preferably 2 to 500, more preferably 2 to 100, even more preferably 5 to 100, and particularly preferably 5 to 50.

[0101] In a preferred embodiment, formula (III) above is the following formula (IIIa): [ka] [In formula: R 31 , R 32 , R 33 , and R 34 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, A 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group, n² is any integer. It is represented as follows.

[0102] In a preferred embodiment, R 31 and R 32 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 33 , and R 34 This is a hydrogen atom.

[0103] In a more preferred embodiment, R 31 and R 32 C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 33 , and R 34This is a hydrogen atom.

[0104] The polyimide compound represented by formula (III) above can be obtained by polymerizing a dicarboxylic acid having an amino group or its anhydride.

[0105] For example, the compound represented by formula (IIIa) above is represented by the following formula (VI): [ka] [In formula: R 31 , R 32 , R 33 , and R 34 These are, independently, hydrogen atoms and C 1-6 Alkyl alkyl group, C 1-6 It is an alkoxy group or a halogen atom, A 4 C is a linear or branched chain. 4-16 It is a perfluoroalkylene group. It can be obtained by polymerizing the compound represented by .

[0106] The compound represented by formula (VI) above, due to the presence of both a phthalic anhydride moiety and a benzene ring moiety, exhibits polarization in the direction of the molecular main chain and can therefore have high solubility.

[0107] In a preferred embodiment, R in formula (VI) above 31 , and R 32 Each of them is independent of C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 33 , and R 34 This is a hydrogen atom.

[0108] In a more preferred embodiment, R of formula (VI) 31 , and R 32 C 1-6 Alkyl alkyl group, C 1-6 An alkoxy group or a halogen atom, R 33 , and R 34 This is a hydrogen atom.

[0109] The polyimide compounds represented by formula (I) and formula (III) of this disclosure can be used in a variety of applications.

[0110] Examples of the above applications include automotive components, aircraft components, electrical and electronic components, paints, adhesives, and the like.

[0111] The polyimides of this disclosure, as well as their manufacturing methods and intermediates, have been described in detail above. However, the uses and manufacturing methods of the polyimides of this disclosure are not limited to those exemplified above. [Examples]

[0112] The polyimides of this disclosure will be described in more detail through the following examples, but the present invention is not limited to these examples.

[0113] Example 1 [ka]

[0114] To a 2 mL solution of dodecafluoro-1,6-diiodohexane (0.3 mmol, 70 μL) in dichloromethane, 10 equivalents of 2,6-xylidine(1), 5 equivalents of cesium carbonate, and 10 equivalents (1 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm wavelength LED under air. As a result, the target diamine compounds 2a and 2b were obtained in 60% and 15% yields, respectively.

[0115] Diamine compound 2a: 1 H NMR (400MHz, CDCl3) δ= 7.13 (4H, s), 3.85 (4H, br s), 2.20 (12H, s). 19 F NMR (376MHz, CDCl3) δ= -109.6 (4F, s), -121.9 (4F, s), -122.3 (4F, s). 13 C NMR (150MHz, CDCl3) δ= 145.9, 126.7, 121.0, 117.6 (t, J = 24.0 Hz), 18.0. Diamine compound 2b: 1 H NMR (400MHz, CDCl3) δ= 7.14 (2H, s), 7.03 (1H, d, J = 8.2 Hz), 6.93 (1H, d, J = 8.2 Hz), 3.86 (2H, br s), 3.74 (2H, br s), 2.22 (6H, s), 2.21 (6H, s). 19 F NMR (376MHz, CDCl3) δ= -104.5 (2F, s), -109.6 (2F, s), -121.0 (2F, s), -121.8 (2F, s), -122.1 (2F, s), -122.2 (2F, s). 13 C NMR (150MHz, CDCl3) δ= 145.9, 144.0, 131.6, 127.6, 126.7, 121.0, 118.4 - 117.5 (m), 18.1, 17.6.

[0116] Example 2 [ka]

[0117] To a 4 mL solution of dodecafluoro-1,6-diiodohexane (0.3 mmol, 70 μL) in dichloromethane, 10 equivalents of 2,6-xylidine(1), 1.5 equivalents of cesium carbonate, and 5 equivalents (2 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm wavelength LED under air. As a result, the target diamine compounds 2a and 2b were obtained in 60% and 21% yields, respectively.

[0118] Example 3 [ka]

[0119] To a 5 mL solution of dodecafluoro-1,6-diiodohexane (0.6 mmol, 335.6 mg) in dichloromethane, 5 equivalents of 2,6-xylidine(1), 1.5 equivalents of cesium carbonate, and 5 equivalents (4 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm LED under air for 48 hours. As a result, the target diamine compounds 2a (56%) and 2b (20%) were obtained in yield.

[0120] Example 4 [ka]

[0121] To a 20 wt% solution (DMF) of 4,4'-oxydiphthalic anhydride (3) (0.13 mmol, 41.2 mg), diamine compound (2a) was added in equimolar amounts, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, polyimide 4a with a number average molecular weight of 13,000 was obtained in 78% yield. At each reaction time, the formation of the target PAA (polyamic acid) intermediate, PI (polyimide), was confirmed. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0122] Polyimide 4a: 1 H NMR (400MHz, CDCl3) δ= 8.05 (2H, d, J = 8.2 Hz), 7.59 (2H, s), 7.56 (2H, d, J = 8.2 Hz), 7.44 (4H, s), 2.26 (12H, s). 19 F NMR (376MHz, CDCl3) δ= -111.2 (4F, s), -121.7 (8F, s).

[0123] Example 5 [ka]

[0124] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.19 mmol, 101.3 mg), an equimolar amount of diamine compound (2b) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, polyimide 4b with a number-average molecular weight of 6400 was obtained in 56% yield. At each reaction time, the formation of the target PAA (polyamic acid) intermediate and PI (polyimide) was confirmed.

[0125] Polyimide 4b: 1 H NMR (500MHz, CDCl3) δ= 8.05 (2H, d, J = 8.3 Hz), 7.61-7.55 (5H, m), 7.43 (2H, s), 7.34 (1H, d, J = 7.7 Hz), 2.24-2.21 (12H, m). 19 F NMR (471MHz, CDCl3) δ= -105.3 (2F, s), -111.2 (2F, s), -120.9 (2F, s), -121.3--121.6 (4F, m), -122.0 (2F, s).

[0126] Example 6 [ka]

[0127] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.25 mmol, 77.5 mg), an equimolar mixture of diamine compounds (2a:2b=49:51) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, polyimide 4ab with a number-average molecular weight of 8400 was obtained in 62% yield (entry 2). At this time, the formation of the target PAA (polyamic acid) intermediate and PI (polyimide) was confirmed at each reaction time.

[0128] Polyimide 4ab: 1 H NMR (500MHz, CDCl3) δ= 8.05 (d, J = 8.3 Hz), 7.61-7.55 (m), 7.43 (s), 7.34 (d, J = 7.7 Hz), 2.24-2.21 (12H, m). 19 F NMR (471MHz, CDCl3) δ= -105.3 (s), -111.2 (s), -120.9 (s), -121.3--121.6 (m), -122.0 (s).

[0129] Example 7 [ka]

[0130] To a 2.5 mL solution of perfluoro-1,8-diiodoctane (0.3 mmol, 191.4 mg) in dichloromethane, 5 equivalents of 2,6-xylidine(1), 3 equivalents of cesium carbonate, and 5 equivalents (2 mL) of aqueous sodium thiosulfate solution were added, and the mixture was irradiated with a 365 nm LED under air for 24 hours. As a result, the target diamine compounds 5a and 5b were obtained in 53% and 17% yields, respectively.

[0131] Diamine compound 5a: 1H NMR (500MHz, CDCl3) δ= 7.13 (4H, s), 3.87 (4H, br s), 2.20 (12H, s). 19 F NMR (471MHz, CDCl3) δ= -109.7 (4F, s), -121.8 (4F, s), -122.3 (8F, s). 13 C NMR (150MHz, CDCl3) δ= 146.0, 126.7, 121.0, 117.4 (t, J = 24.0 Hz), 17.7. ジアミン compound 5b: 1 H NMR (500MHz, CDCl3) δ= 7.14 (2H, s), 7.04 (1H, d, J = 8.0 Hz), 6.93 (1H, d, J = 8.0 Hz), 3.81 (4H, br s), 2.22-2.21 (12H, m). 19 F NMR (471MHz, CDCl3) δ= -104.5 (2F, s), -109.7 (2F, s), -121.0 (2F, s), -121.8 (2F, s), -122.0 (2F, s), -122.3 (6F, s). 13 C NMR (150MHz, CDCl3) δ= 146.0, 144.1, 127.6, 126.7, 125.5, 121.0, 117.9, 117.4 (t, J = 24.0 Hz), 18.1, 17.7, 14.0.

[0132] Example 8

change

[0133] To a 2.5 mL solution of dodecafluoro-1,6-diiodohexane (0.3 mmol) in dichloromethane, 10 equivalents of 2,6-difluoroaniline (6), 3 equivalents of cesium carbonate, and 5 equivalents (2 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm LED under air for 72 hours. As a result, the target diamine compounds 7a (42%) and 7b (11%) were obtained in yield.

[0134] Diamine compound 7a: 1 H NMR (500MHz, CDCl3) δ= 7.07 (4H, dd, J = 6.7, 1.9 Hz), 4.07 (4H, br s). 19 F NMR (471MHz, CDCl3) δ= -109.9 (4F, s), -121.9 (4F, s), -122.5 (4F, s), -131.8 (4F, s). Diamine compound 7b: 1 H NMR (500MHz, CDCl3) δ= 7.07 (2H, dd, J = 6.7, 1.9 Hz), 6.92 (1H, t, J = 9.3 Hz), 6.86-6.84 (1H, m), 4.07 (2H, br s), 3.90 (2H, br s). 19 F NMR (471MHz, CDCl3) δ= -109.3 (2F, s), -109.9 (2F, s), -121.9 (2F, s), -122.2 (2F, s), -122.5 (2F, s), -122.5 (2F, s), -126.0 (1F, s), -131.0 (1F, s), -131.8 (2F, s).

[0135] Example 9 [ka]

[0136] To a 5 mL solution of perfluoro-1,8-diiodoctane (0.6 mmol, 163.3 mg) in dichloromethane, 5 equivalents of 2,6-difluoroaniline (6X), 3 equivalents of cesium carbonate, and 5 equivalents (4 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm LED under air for 72 hours. As a result, the target diamine compounds 8a (26%) and 8b (12%) were obtained in yield.

[0137] Diamine compound 8a: 1 H NMR (500MHz, CDCl3) δ= 7.07 (4H, dd, J = 6.6, 2.0 Hz), 4.08 (4H, br s). 19 F NMR (471MHz, CDCl3) δ= -109.9 (4F, s), -121.8 (4F, s), -122.4 (8F, s), -131.7 (4F, s). Diamine compound 8b: 1 H NMR (500MHz, CDCl3) δ= 7.07 (2H, dd, J = 6.6, 1.7 Hz), 6.93 (1H, t, J = 9.6 Hz), 6.87-6.84 (1H, m), 4.08 (2H, br s), 3.91 (2H, br s). 19 F NMR (471MHz, CDCl3) δ= -109.3 (2F, s), -109.9 (2F, s), -121.8 (2F, s), -122.1 (2F, s), -122.4 (12F, s), -125.9 (1F, s), -131.0 (1F, s), -131.7 (2F, s).

[0138] Example 10 [ka]

[0139] To a 2.5 mL solution of perfluoro-1,6-diiodohexane (0.3 mmol, 159.6 mg) in dichloromethane, 5 equivalents of 5-aminoindole(9), 3 equivalents of cesium carbonate, and 5 equivalents (2 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm LED under air for 48 hours. As a result, the target diamine compound was obtained in a yield of 26%.

[0140] Diamine compounds: 1 H NMR (500MHz, CDCl3) δ= 8.08 (2H, br s), 7.31 (2H, d, J = 8.6 Hz), 7.16 (2H, t, J = 2.9 Hz), 6.60 (2H, d, J = 8.6 Hz), 6.56 (2H, s), 4.03 (4H, br s). 19 F NMR (471MHz, CDCl3) δ= -106.1 (4H, s), -122.1 (4H, s), -122.4 (4H, s).

[0141] Example 11 (Synthesis of diethyl monomer) [ka]

[0142] To a 2.5 mL solution of dodecafluoro-1,6-diiodohexane (0.3 mmol) in dichloromethane, 5 equivalents of 2,6-diethylaniline (10), 1.5 equivalents of cesium carbonate, and 5 equivalents (2 mL) of aqueous sodium thiosulfate solution were added, and the mixture was irradiated with a 365 nm LED under air for 24 hours. As a result, the target diamine compound 11 was obtained in 50% yield.

[0143] Diamine compound 11 1H NMR (500MHz, CDCl3) δ= 7.15 (4H, s, PhH), 3.93 (4H, br s, PhNH2), 2.54 (8H, q, J = 7.5, PhCH2CH3), 1.27 (12H, t, J = 7.6, PhCH2CH3). 19 F NMR (471MHz, CDCl3) δ= -109.7 (4F, s, PhCF2), -121.9 (4F, s, CF2), -122.3 (4F, s, CF2)

[0144] Example 12 (Synthesis of dichloromonomers) [ka]

[0145] To a 2.5 mL solution of dodecafluoro-1,6-diiodohexane (0.3 mmol) in dichloromethane, 5 equivalents of 2,6-dichloroaniline (12), 3 equivalents of cesium carbonate, and 5 equivalents (2 mL) of sodium thiosulfate aqueous solution were added, and the mixture was irradiated with a 365 nm LED under air for 72 hours. As a result, the target diamine compounds 13a and 13b were obtained in a production ratio of 73:27.

[0146] Diamine compound 13a (pp form) 1 H NMR (500MHz, CDCl3) δ= 7.39 (4H, s, PhH), 4.80 (4H, br s, PhNH2). 19 F NMR (471MHz, CDCl3) δ= -110.1 (4F, s, PhCF2), -121.8 (4F, s, CF2), -122.1 (4F, s, CF2)

[0147] Diamine compound 13b (pm form) 1H NMR (500MHz, CDCl3) δ= 7.39 (2H, s, PhH), 7.29 (1H, d, J = 8.6 Hz, PhH), 6.92 (1H, d, J = 8.6 Hz, PhH), 4.80 (2H, br s, PhNH2), 4.74 (2H, br s, PhNH2). 19 F NMR (471MHz, CDCl3) δ= -107.2 (2F, s, PhCF2), -110.1 (2F, s, PhCF2), -120.5 (2F, s, CF2), -121.8 (2F, s, CF2), -122.1 (4F, s, CF2)

[0148] Example 13 [ka]

[0149] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.13 mmol, 41.2 mg), an equimolar amount of diamine compound (7) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 1.3 × 10⁶. 4 Polyimide 14 was obtained in 50% yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0150] Polyimide 14: 19 F NMR (471MHz, CDCl3) δ= -111.4 (4F, s), -122.1 (8F, s), -132.0 (4F, s)

[0151] Example 14 [ka]

[0152] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.25 mmol, 76.7 mg), an equimolar amount of diamine compound (11) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 3.7 × 10⁶. 3 Polyimide 15 was obtained in 85% yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0153] Polyimide 15: 1 H NMR (500MHz, CDCl3) δ= 8.06 (2H, d, J = 8.0), 7.59-7.56 (4H, m), 7.48 (4H, s), 2.57-52 (8H, m), 1.21-1.17 (12H, m). 19 F NMR (471MHz, CDCl3) δ= -111.2 (4F, s), -121.7 (8F, s).

[0154] Example 15 [ka]

[0155] To a solution of 1,8-diiodoperfluorooctane (0.6 mmol, 784.2 mg) in dichloromethane (4 mL), 5 equivalents (897.0 mg) of 2,6-diethylaniline, 5 equivalents (947.2 mg in 4 mL of water) of aqueous sodium thiosulfate, and 1.5 equivalents (587.4 mg) of cesium carbonate were added, and the mixture was irradiated with a 365 nm LED under air for 48 hours. As a result, the target diamine compounds 16a and 16b were obtained with NMR yields of 71% and 5%, respectively.

[0156] Diamine compound 16a: 1H NMR (500MHz, CDCl3) δ= 7.15 (4H, s), 3.94 (4H, s), 2.54 (8H, q, J = 7.4), 1.28 (12H, t, J = 7.6). 19 F NMR (471MHz, CDCl3) δ= -109.7 (4F, s), -121.8 (4F, s), -122.3 (4F, s), -122.3 (4F, s) Diamine compound 16b: 19 F NMR (471MHz, CDCl3) δ= -104.2 (2F, s), -109.7 (2F, s), -121.7 (2F, s), -121.8 (4F, s), -122.3 (6F, s)

[0157] Example 16 [ka]

[0158] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.23 mmol, 69.9 mg), an equimolar amount of diamine compound (16a) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 5.2 × 10⁶. 3 Polyimide 17 was obtained in 73% yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0159] Polyimide 17: 1 H NMR (500MHz, CDCl3) δ= 8.06 (2H, d, J = 8.0), 7.59-7.57 (4H, m), 7.47 (4H, s), 2.57-52 (8H, m), 1.21-1.17 (12H, m). 19F NMR (471MHz, CDCl3) δ= -111.0 (4F, s), -121.7 (8F, s).

[0160] Example 17 [ka]

[0161] To a solution of 1,6-diiodoperfluorohexane (0.6 mmol, 140 μL) in dichloromethane (5 mL), 5 equivalents (411 mg) of 2-methoxy,6-methylaniline, 5 equivalents (474 ​​mg in 4 mL of water) of aqueous sodium thiosulfate, and 1.5 equivalents (587.4 mg) of cesium carbonate were added, and the mixture was irradiated with a 365 nm LED under air for 48 hours. As a result, the target diamine compound 19a was obtained in 68% yield, and a mixture of 19b and 19c in 21% yield.

[0162] Diamine compound 19a: 1 H NMR (500MHz, CDCl3) δ= 6.94 (2H, s), 6.83 (2H, s), 4.04 (4H, br s), 3.87 (6H, s), 2.20 (6H, s). 19 F NMR (471MHz, CDCl3) δ= -109.4 (4F, s), -121.9 (4F, s), -122.3 (4F, s). A mixture of diamine compounds 19b and 19c: 1 H NMR (500MHz, CDCl3) δ= 6.98 (1H, d, J = 9.2), 6.74 (1H, d, J = 9.2), 4.04 (4H, br s), 3.89 (6H, s), 2.22 (6H, s). 19 F NMR (471MHz, CDCl3) δ= -104.0 (2F, s), -109.4 (2F, s), -121.0 (2F, s) -121.9 (2F, s), -122.3 (4F, s).

[0163] Example 18 [ka]

[0164] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.50 mmol, 155.1 mg), an equimolar amount of diamine compound (19) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 4.6 × 10⁶. 3 Polyimide 20 was obtained in 79% yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0165] Polyimide 20: 1 H NMR (500MHz, CDCl3) δ= 8.03 (2H, d, J = 6.6), 7.57-7.52 (4H, m), 7.21 (2H, s), 7.05 (2H, s), 3.83-3.82 (6H, m), 2.29-2.27 (6H, m). 19 F NMR (471MHz, CDCl3) δ= -115.4 (4F, s), -127.6 (8F, s).

[0166] Example 19 [ka]

[0167] To a 20 wt% DMF solution of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride 21 [commonly known as 6FDA] (0.27 mmol, 117.0 mg), an equimolar amount of diamine compound (11) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 2.5 × 10⁶.3 Polyimide 22 was obtained in 60% yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film. This polyimide film was insoluble in AK-225 (1 mol / L).

[0168] Polyimide 22: 1 H NMR (500MHz, CDCl3) δ= 8.09 (2H, d, J = 8.2), 7.99 (4H, m), 7.49 (4H, s), 2.54 (8H, m), 1.20 (12H, t, J = 7.6). 19 F NMR (471MHz, CDCl3) δ= -63.6 (6F, s), -111.3 (4F, s), -121.8 (8F, s).

[0169] Example 20 [ka]

[0170] To a 20 wt% DMF solution of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride 21 [commonly known as 6FDA] (0.199 mmol, 88.5 mg), an equimolar amount of diamine compound (2a) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 6.3 × 10⁶. 3 Polyimide 23 was obtained in 95% yield.

[0171] Polyimide 23: 1 H NMR (500MHz, CDCl3) δ= 8.09 (2H, d, J = 7.8), 7.99 (4H, m), 7.45 (4H, s), 2.27 (12H, s). 19F NMR (471MHz, CDCl3) δ= -63.6 (6F, s), -111.3 (4F, s), -121.7 (8F, s).

[0172] Example 21 [ka]

[0173] To a 25 / 5 mL acetonitrile / water mixture of dodecafluoro-1,6-diiodohexane (1.0 mmol), 6 equivalents of 2,6-diisopropylaniline (24), 10 mol% eosin Y-2Na, 2.5 equivalents of cesium carbonate, and 4 equivalents of ascorbic acid (2 mL) were added, and the mixture was irradiated with white LED light under an argon atmosphere for 24 hours. As a result, the target diamine compound 25 was obtained in 68% yield.

[0174] Diamine compound 25: 1 H NMR (500MHz, CDCl3) δ= 7.19 (4H, s), 4.02 (4H, br s), 2.90 (2H, m), 1.28 (6H, d, J = 6.9). 19 F NMR (471MHz, CDCl3) δ= -109.8 (4F, s), -121.9 (4F, s), -122.3 (4F, s).

[0175] Example 22 [ka]

[0176] To a 50 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.50 mmol, 155.9 mg), an equimolar amount of diamine compound (25) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 2.3 × 10⁶. 4Polyimide 6 was obtained. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0177] Polyimide 25: 1 H NMR (500MHz, CDCl3) δ= 8.07 (2H, d, J = 9.2), 7.60 (4H, m), 7.51 (4H, s), 7.40 (4H, d, J = 7.3), 2.79 (4H, m), 1.21 (24H, m). 19 F NMR (471MHz, CDCl3) δ= -111.5 (4F, s), -121.9 (8F, s).

[0178] Example 23 [ka]

[0179] To a 50 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.50 mmol, 155.8 mg), an equimolar amount of diamine compound (8) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 5.3 × 10⁶. 3 Polyimide 27 was obtained. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0180] Example 24 [ka]

[0181] To a 50 wt% DMF solution of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride 21 [commonly known as 6FDA] (0.51 mmol, 225.4 mg), an equimolar amount of diamine compound (8) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 6.7 × 10⁶. 3 Polyimide 28 was obtained in yield. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and then at 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film.

[0182] Polyimide 28: 1 H NMR (500MHz, CDCl3) δ= 8.11 (2H, d, J = 8.2), 8.01 (2H, s), 7.93 (2H, d, J = 8.2), 7.40 (4H, d, J = 7.3). 19 F NMR (471MHz, CDCl3) δ= -63.6 (6F, s), -111.3 (4F, s), -112.3 (4F, s), -121.7 (6F, s), 122.2 (6F, s).

[0183] Example 25 [ka]

[0184] To a 50 wt% DMF solution of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride 21 [commonly known as 6FDA] (0.50 mmol, 223.0 mg), an equimolar amount of diamine compound (7) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. As a result, the number average molecular weight was 6.1 × 10⁶. 3Polyimide 29 was obtained. The product was dissolved in DMF, spin-coated onto a quartz plate, and heat-treated at 70°C for 0.5 hours and 260°C for 1.5 hours to obtain a pale yellow transparent polyimide film. This polyimide film was completely soluble in AK-225 (1 mol / L). From a comparison with Example 19, it is considered that this solubility was due to the fluorine atoms on the aromatic ring.

[0185] Polyimide 29: 1 H NMR (500MHz, CDCl3) δ= 8.11 (2H, d, J = 7.8), 8.03 (2H, s), 7.93 (2H, d, J = 7.8), 7.40 (4H, d, J = 6.9). 19 F NMR (471MHz, CDCl3) δ= -63.7 (6F, s), -111.3 (4F, s), -112.4 (4F, s), -121.7 (8F, s).

[0186] Comparative Example 1 [ka]

[0187] For the physical properties and characteristics of polyimide 30 described above, please refer to Polymer Preprints, Japan vol.69, No.2(2020) 3R05.

[0188] Comparative Example 2 [ka]

[0189] To a 20 wt% DMF solution of 4,4'-oxydiphthalic anhydride (3) (0.300 mmol, 93.0 mg), 2,2'-bis(4-aminophenylhexafluoropropane 31) (0.300 mmol, 100 mg) was added, and the mixture was stirred under an argon atmosphere at 50°C for 50 hours, followed by 14 hours at 80°C, 24 hours at 110°C, and 24 hours at 140°C. After the reaction was complete, the product precipitated without dissolving in the reaction solvent, DMF. The presence of the polymer was visually confirmed. The solvent was removed from the resulting reaction mixture, and THF (tetrahydrofuran) was added, causing partial dissolution of the polymer. The THF-soluble components were reprecipitation, and the THF-insoluble components were purified by washing, yielding 10% THF-soluble polyimide 32 and 21% THF-insoluble polyimide 32 in yield. GPC analysis was performed on the THF-soluble components, and their number-average molecular weight was 4.9 × 10⁶. 3 That was the case.

[0190] The various physical properties of the compounds obtained in the examples are summarized in the table below. [Table 1]

[0191] (evaluation) Film production: The polyimide obtained in each example was dissolved in DMF (1 mL), the resulting solution was dropped onto a quartz plate, treated with a spin coater, and then heat-treated at 70°C for 0.5 hours and 260°C for 1.5 hours to produce a polyimide film.

[0192] Measurement of refractive index n: Using thin films fired on a silicon substrate, TE and TM measurements were performed at measurement wavelengths of 633, 850, 1550, and 3120 nm using a prism coupler (METRCON PC-2010).

[0193] Calculation of dielectric constant: The calculation was performed using the following formula. Dielectric constant ε=1.1×[Refractive index n(@588nm)] 2 [Industrial applicability]

[0194] The polyimide compounds disclosed herein can be used in a wide range of applications, including automotive components, aircraft components, and electrical and electronic components.

Claims

1. The following formula (Ia'): 【Chemistry 1】 [In the formula: R11, R12, R15, and R16 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom. R13, R14, R17, and R18 are hydrogen atoms. A1 is a linear or branched C6-8 perfluoroalkylene group, A2 is an aliphatic or aromatic bisimide-N',N-diyl, n1 is any integer. A polyimide compound represented by the formula.

2. R １１ and R １２ R is a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom. １５ and R １６ The polyimide compound according to claim 1, wherein is a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom.

3. A2 is the following formula: 【Chemistry 2】 [In the formula: A ３ [where n1 is an arbitrary integer, and n1 is a single bond or a divalent organic group.] A polyimide compound according to claim 1 or 2, wherein the group is represented by .

4. A ３ C may be substituted with single, linear, or branched fluorine atoms. １－１６ Alkylene group, oxygen atom, -CO-, -C≡C-, -SO ２ - 【Transformation 3】 The polyimide compound according to claim 3.

5. A ２ is the following group: 【Chemistry 4】 【Transformation 5】 The polyimide compound according to any one of claims 1 to 4.

6. Formula (II) below: 【Transformation 6】 [In the formula: Ar １ The formula is as follows: 【Transformation 7】 [In the formula, R11 and R12 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom, and R13 and R14 are hydrogen atoms.] It is a base represented by, Ar² is given by the following formula: 【Transformation 8】 [In the formula, R15 and R16 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom, and R17 and R18 are hydrogen atoms.] It is a base represented by, A １ This is a linear or branched C6-8 perfluoroalkylene group, A ３ It is a divalent organic group, n1 is any integer. A compound represented by the formula.

7. The following formula (IVa): 【Chemistry 9】 [In the formula: R11, R12, R15, and R16 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom. R13, R14, R17, and R18 are hydrogen atoms. A １ This is a linear or branched C6-8 perfluoroalkylene group. A diamine compound represented by [the specified symbol].

8. R １１ , R １２ , R １５ and R １６ The diamine compound according to claim 7, wherein is a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom.

9. The above formula (IVb): 【Chemistry 10】 [In the formula: R11, R12, R15, and R16 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom. R13, R14, R17, and R18 are hydrogen atoms. A １ This is a linear or branched C6-8 perfluoroalkylene group. A method for producing a diamine compound represented by the following: The following formula (VII): H-Ar ４ -NH ２ [In the formula, Ar ４ The formula is as follows: 【Transformation 8】 [In the formula: R11, R12, R15, and R16 are each independently a C1-3 alkyl group, a C1 alkoxy group, a fluorine atom, or a chlorine atom, and R13, R14, R17, and R18 are hydrogen atoms.] It is a base represented by one of the following: A compound represented by the following formula (VIII): I-A １ -I [In the formula, A １ This is a linear or branched C6-8 perfluoroalkylene group. A method for producing a compound represented by under light irradiation.

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