JP7093008B2 - Method for Producing Fluorine-Containing Aromatic Diamine - Google Patents

Description

The present invention relates to a method for producing a fluorinated aromatic diamine, a method for producing a fluorinated aromatic polyimide, and a method for producing a fluorinated aromatic polyamide. Fluoro-containing aromatic diamines are raw materials for polyimides known as engineering plastics having excellent physical properties such as heat resistance, and these polyimides are used in various industrial fields.

Polyimide is used in many industrial fields as a material for electronic devices, fuel cell materials, medical materials, gas separation membranes, automobile parts, aircraft parts, space equipment parts, and the like.

Polyimide is usually synthesized by synthesizing a polyamic acid using a diamine and a tetracarboxylic dianhydride, and then dehydrating and closing the ring of the precursor polyamic acid by heating or the like (hereinafter, referred to as imidization). be).

Polyimide, which is usually in a state after imidization, is insoluble in organic solvents. Therefore, in order to obtain a polyimide molded product, a polyamic acid before imidization is dissolved in an organic solvent (hereinafter, may be referred to as varnish), applied to a substrate, molded, and then imidized to form a polyimide. The body is being done. However, the method of applying the varnish to the substrate, forming the film, and then imidizing the polyamic acid in the varnish to obtain the polyimide film requires imidization after the application by heating or a chemical reaction, which complicates the process. There is a problem of becoming. Further, also in the storage of varnish, there is a problem that the polyamic acid in the varnish is easily denatured at room temperature and lacks storage stability, and must be stored in a freezer by cooling to prevent denaturation.

Therefore, there is a demand for a polyimide that can be dissolved in an organic solvent in the state of polyimide, instead of dissolving polyamic acid, which is a precursor of polyimide, in an organic solvent.

As a means for making it soluble in an organic solvent in the state of polyimide, in aromatic polyimides, a hexafluoroisopropanol group (-C (CF ₃ )) is attached to the aromatic ring in the structure in order to improve the affinity with the organic solvent. It is known that ₂ OH (hereinafter sometimes referred to as HFIP group) is bonded and introduced. Hereinafter, a fluorine-containing aromatic polyimide obtained by binding an HFIP group to an aromatic ring in the structure may be referred to as an HFIP group-containing polyimide.

For example, Patent Documents 1 to 4 use HFIP group-containing polyimides having a structure in which diamine, which is an aromatic polycyclic compound containing two or more aromatic rings, is used as a raw material and HFIP groups are bonded to each aromatic ring. The gas separation membrane is disclosed. Patent Documents 1 to 4 describe that the HFIP group-containing polyimide becomes soluble in an organic solvent by introducing an HFIP group into the structure, and then can be formed into a film by being applied to a substrate. ing.

Further, Patent Document 5 discloses an HFIP group-containing polyimide having a fluorescent property, which is obtained by bonding an HFIP group and an alkyl group or a halogen group to each aromatic ring using diamine, which is an aromatic polycyclic compound, as a raw material. ing. Patent Document 5 describes that the HFIP group-containing polyimide becomes soluble in an organic solvent by introducing an HFIP group into the structure and can be formed into a film by casting a polyimide solution.

The HFIP group-containing polyimides described in Patent Documents 1 to 5 use diamine, which is an aromatic polycyclic compound in which an HFIP group is bonded to each aromatic ring, as a raw material and react with a tetracarboxylic acid dianhydride to obtain a polyamic acid. After being obtained, it is synthesized by imidization. Hereinafter, the fluorine-containing aromatic diamine obtained by binding HFIP to the aromatic ring in the structure may be referred to as an HFIP group-containing diamine.

Patent Documents 5 to 7 disclose HFIP group-containing diamines and methods for producing the same. In Patent Documents 5 to 7, aromatic diamine is reacted with hexafluoroacetone trihydrate (hereinafter, may be referred to as HFA trihydrate) or hexafluoroacetone (hereinafter, may be referred to as HFA). It is described that an HFIP group-containing diamine can be obtained by substituting a hydrogen atom bonded to an aromatic ring of an aromatic diamine with an HFIP group.

（式中、Ａは、単結合、酸素原子、硫黄原子、ＣＯ、ＣＨ_２、ＳＯ、ＳＯ_２、Ｃ（ＣＨ_３）_２、ＮＨＣＯ、Ｃ（ＣＦ_３）_２ 、フェニレン、脂環を表し、Ｒ^１は、それぞれ独立に
、水素原子、炭素数１～４のアルキル基、またはハロゲン原子であり、ａとｂはそれぞれ独立に０～２の整数を表し、１≦ ａ＋ｂ≦４である。） Patent Documents 5 and 6 describe the following reactions for obtaining an HFIP group-containing diamine from a diamine which is an aromatic polycyclic compound and HFA or HFA trihydrate.

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , NHCO, C (CF ₃ ) ₂ , phenylene, and an alicyclic, R. ¹ is an independent hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and a and b independently represent an integer of 0 to 2, and 1 ≦ a + b ≦ 4).

Patent Document 5 discloses a method for obtaining an HFIP group-containing polyimide from the HFIP group-containing diamine, which is the aromatic polycyclic compound, via an HFIP-containing polyamic acid.

Further, Patent Document 6 discloses a method for obtaining an HFIP-containing polyamide from the above-mentioned HFIP group-containing diamine, and a method for cyclizing and condensing the HFIP-containing polyamide.

（式中、ｃは、１～４の整数を表す。） Patent Document 7 describes the following reaction for obtaining an HFIP group-containing diamine from a diamine which is an aromatic monocyclic compound and HFA or HFA trihydrate.

(In the formula, c represents an integer of 1 to 4.)

Patent Document 7 discloses a method for obtaining an HFIP group-containing polyimide from the HFIP group-containing diamine, which is the aromatic monocyclic compound, via an HFIP-containing polyamic acid. Further, a method for obtaining an HFIP-containing polyamide from the HFIP group-containing diamine which is the aromatic monocyclic compound, and a method for cyclizing and condensing the HFIP-containing polyamide are disclosed.

Patent Documents 5 to 7 describe that the reaction solvent for the reaction for obtaining the HFIP-containing diamine can be carried out without using a solvent, but a solvent can also be used. Examples of the solvent used are benzene, toluene, xylene, nitrobenzene or benzonitrile.

Further, in Patent Documents 5 to 7, when an aromatic diamine is reacted with HFA or HFA trihydrate to obtain an HFIP group-containing diamine, a catalyst may not be used, but the reaction is promoted by using an acid catalyst. It is stated that it is preferable to let it. Acid catalysts used include aluminum chloride, iron (III) chloride, boron fluoride, benzenesulfonic acid, camphorsulfonic acid (CAS), methanesulfonic acid, p-toluenesulfonic acid (p-TsOH), paratoluenesulfonic acid. Monohydrate (p-TsOH · _H2O ) or pyridinium paratoluenesulfonic acid (PPTS) is exemplified.

In the examples of Patent Documents 1 to 7, when the aromatic diamine is reacted with HFA or HFA trihydrate to obtain an HFIP group-containing diamine, a solvent-free reaction solvent, toluene or xylene is used as the reaction solvent, and the catalyst is para. Toluenesulfonic acid monohydrate (p-TsOH · _H2O ) is used.

（式中、Ｒ²は、単結合、酸素原子、硫黄原子、－Ｃ(＝Ｏ)－基、－ＣＨ_２－基、－Ｓ(＝Ｏ)－基、－Ｓ(＝Ｏ)_２－、－Ｃ(ＣＨ_３)_２－基、－ＮＨ(Ｃ＝Ｏ)－基もしくは－Ｃ(ＣＦ_３)_２－基、または脂環、複素環もしくは芳香環を有する２価の有機基である。ＨＦＩＰ
は－Ｃ(ＣＦ_３)_２ＯＨ基を表す。） Further, Patent Document 8 describes that the following asymmetric aromatic diamine as a raw material is reacted with HFA3 hydrate to synthesize a corresponding HFIP group-containing diamine in the same manner as in Patent Documents 5 to 7. ing.

(In the formula, R ² is a single bond, oxygen atom, sulfur atom, -C (= O) -group, -CH _2- group, -S (= O) -group, -S (= O) _2- , -C (CH ₃ ) ₂ -group, -NH (C = O) -group or -C (CF ₃ ) ₂ -group, or a divalent organic group having an alicyclic, heterocyclic or aromatic ring.
Represents a -C (CF ₃ ) ₂ OH group. )

（式中、Ｒ³は、水素原子、フッ素原子、塩素原子、臭素原子、炭素数１～４のアルキル基、任意の数の水素原子がフッ素に置換された炭素数１～４のアルキル基、フェニル基、メトキシ基、ニトロ基からなる群から選ばれる１種の置換基を表す。Ｒ⁴は、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ナフチル基、ビフェニル基、スルホン酸基、－Ｃ≡Ｃ－Ｃ(ＣＨ_３)_２ＯＨ基、－Ｃ≡Ｃ－Ｃ_６Ｈ_５基、－Ｃ≡Ｃ－Ｓｉ（ＣＨ_３）_３基からなる群から選ばれる１種の置換基を表す。ＨＦＩＰは－Ｃ(ＣＦ_３)_２ＯＨ基を表す。） Patent Document 9 describes that, in the same manner as in Patent Documents 5 to 7, an aromatic diamine having the following fluorene skeleton as a raw material is reacted with HFA3 hydrate to synthesize a corresponding HFIP group-containing diamine. Has been done.

(In the formula, R ³ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms in which an arbitrary number of hydrogen atoms are replaced with fluorine. Represents one substituent selected from the group consisting of a phenyl group, a methoxy group and a nitro group. R ⁴ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One selected from the group consisting of sulfonic acid group, -C≡C-C (CH ₃ ) ₂ OH group, -C≡C-C ₆ H ₅ group, -C≡C-Si (CH ₃ ) ₃ group Represents a substituent. HFIP represents a -C (CF ₃ ) ₂ OH group.)

（式中、ｍおよびｐは、それぞれ独立に０～２のいずれかの整数でｍ＋ｐ≦２である。ｑは０もしくは１以上の整数である。ｒおよびｓは、それぞれ独立に０～３の整数であり、且つ、（ｒ＋ｓ）は１以上である。但し、少なくとも１つの－Ｃ(ＣＦ_３)_２ＯＨ基は、少なくとも１つの－ＮＨ_２基と、該縮合多環式芳香族炭化水素基を構成する炭素原子のうち、隣接する炭素同士に結合する関係にある。 Patent Document 10 describes that the following HFIP group-containing diamine is synthesized by reacting the corresponding aromatic diamine as a raw material with HFA3 hydrate in the same manner as in Patent Documents 5 to 7.

(In the equation, m and p are each independently an integer of 0 to 2 and m + p ≦ 2. q is an integer of 0 or 1 or more. R and s are independently of 0 to 3, respectively. It is an integer and (r + s) is 1 or more. However, at least one -C (CF ₃ ) ₂ OH group is at least one -NH ₂ group and the condensed polycyclic aromatic hydrocarbon group. Among the carbon atoms constituting the above, there is a relationship in which adjacent carbons are bonded to each other.

は、単環式芳香環もしくは、縮合多環式芳香環を表し、ヘテロ原子としてＮ原子、Ｏ原子またはＳ原子を含んでもよく、Ｎ原子、Ｏ原子またはＳ原子を含む官能基を置換基として有していてもよい。） Also, in the formula, the part expressed by the following formula

Represents a monocyclic aromatic ring or a fused polycyclic aromatic ring, and may contain an N atom, an O atom or an S atom as a hetero atom, and a functional group containing an N atom, an O atom or an S atom is used as a substituent. You may have. )

Japanese Unexamined Patent Publication No. 2013-10096 Japanese Unexamined Patent Publication No. 2014-128787 Japanese Unexamined Patent Publication No. 2014-128788 Japanese Unexamined Patent Publication No. 2016-137484 Japanese Unexamined Patent Publication No. 2014-129340 JP-A-2007-119503 JP-A-2007-119504 Japanese Unexamined Patent Publication No. 2014-125455 Japanese Unexamined Patent Publication No. 2014-129339 Japanese Unexamined Patent Publication No. 2008-150534

In Patent Documents 5 to 7, in the reaction for obtaining an HFIP group-containing diamine from an aromatic diamine and HFA, the amino group of the aromatic diamine or the amino group of the produced HFIP group-containing diamine is as shown in the following reaction formula. It is described that it reacts with HFA to produce imines as a by-product. Further, it is described that the yield of the HFIP group-containing diamine was 33 to 73% in the examples of Patent Documents 5 to 7.

An object of the present invention is to provide a method for producing an HFIP group-containing diamine, which can solve such a problem, suppress by-production of imines, and produce an HFIP group-containing diamine with good selectivity and yield. ..

Further, it is an object of the present invention to provide a method for producing an HFIP group-containing polyimide and a method for producing an HFIP group-containing polyamide using the above method for producing an HFIP group-containing diamine.

As a result of diligent studies, the present inventors have conducted 1,1,1,3,3,3-hexafluoro-2-propanol (HC (CF ₃ )) as a reaction solvent when reacting HFA with aromatic diamines. By using ₂ OH (hereinafter sometimes abbreviated as HFIP), it was surprisingly found that by-production of imines can be suppressed and an HFIP group-containing polyimide can be produced with high selectivity and yield. It was completed (see Examples 1 to 8 in [Example]).

In addition to being able to dissolve aromatic diamine, which is a raw material, HFIP also has an effect as an acid catalyst because it is weakly acidic, and it is presumed that the reaction could proceed rapidly under milder reaction conditions than in the prior art. Furthermore, it is presumed that the rapid progress of the reaction reduced the excess HFA that reacts with the amino group of the raw material or the HFIP group-containing diamine, thereby obtaining the effect of suppressing the by-product of imines. ..

In the present specification, the term diamine or aromatic diamine simply refers to those having no HFIP group.

That is, the present invention includes inventions 1 to 13.
[Invention 1]
Aromatic diamine and
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
A step of obtaining a fluorine-containing aromatic diamine in which a -C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
A method for producing a fluorine-containing aromatic diamine.

（式中、Ａは、単結合、エーテル結合、スルフィド結合、ＣＯ、ＣＨ_２、ＳＯ、ＳＯ_２、Ｃ（ＣＨ_３）_２、もしくはＣ（ＣＦ_３）_２、または脂環、複素環、芳香族複素環もしくは芳香環を有する２価の基であり、Ｒ^１は、それぞれ独立に、水素原子、炭素数１～４のアルキル基、またはハロゲン原子である。）
で表される芳香族ジアミンと、
ヘキサフルオロアセトンを
１，１，１，３，３，３－ヘキサフルオロ－２－プロパノール中で反応させ、
式（２）

（式中、ＡおよびＲ^１は、式（１）における意味と同義であり、ａとｂはそれぞれ独立に０～２の整数を表し、１≦ ａ＋ｂ≦４である。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明１の含フッ素芳香族ジアミンの製造方法。 [Invention 2]
Equation (1)

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
Aromatic diamine represented by
Hexafluoroacetone was reacted in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (2)

(In the equation, A and R ¹ have the same meaning as in the equation (1), and a and b independently represent integers of 0 to 2, and 1 ≦ a + b ≦ 4.)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the first invention.

（式中、ＡおよびＲ^１は、式（１）における意味と同義である）
で表される芳香族ジアミンと、
ヘキサフルオロアセトンを
１，１，１，３，３，３－ヘキサフルオロ－２－プロパノール中で反応させ、式（４）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明２の含フッ素芳香族ジアミンの製造方法。 [Invention 3]
Equation (3)

(In the formula, A and R ¹ are synonymous with the meaning in the formula (1))
Aromatic diamine represented by
Hexafluoroacetone was reacted in 1,1,1,3,3,3-hexafluoro-2-propanol to formula (4).

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the second invention.

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される芳香族ジアミンと、
ヘキサフルオロアセトンを
１，１，１，３，３，３－ヘキサフルオロ－２－プロパノール中で反応させ、
式（６）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明２または発明３の含フッ素芳香族ジアミンの製造方法。 [Invention 4]
Equation (5)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine represented by
Hexafluoroacetone was reacted in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (6)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the second invention or the third invention.

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される芳香族ジアミンと、
ヘキサフルオロアセトンを、
１，１，１，３，３，３－ヘキサフルオロ－２－プロパノール中で反応させ、
式（８）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明２または発明３の含フッ素芳香族ジアミンの製造方法。 [Invention 5]
Equation (7)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine represented by
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (8)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the second invention or the third invention.

で表される芳香族ジアミンと、
ヘキサフルオロアセトンを、
１，１，１，３，３，３－ヘキサフルオロ－２－プロパノール中で反応させ、
式（１０）

（式中、ｃは、１～４の整数を表す。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明１の含フッ素芳香族ジアミンの製造方法。 [Invention 6]
Equation (9)

Aromatic diamine represented by
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (10)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the first invention.

（式中、ｃは、１～４の整数を表す。）
で表される含フッ素芳香族ジアミンを得る工程を含む、
発明６の含フッ素芳香族ジアミンの製造方法。 [Invention 7]
With para-phenylenediamine,
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (11)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to the invention 6.

で表される含フッ素芳香族ジアミンである、
発明７の含フッ素芳香族ジアミンの製造方法。 [Invention 8]
The fluorine-containing aromatic diamine represented by the formula (11)

It is a fluorine-containing aromatic diamine represented by.
The method for producing a fluorine-containing aromatic diamine according to the invention 7.

（式中、ｃは、１～４の整数を表す。）
で表される含フッ素芳香族ジアミン化合物を得る工程を含む、
発明６の含フッ素芳香族ジアミンの製造方法。 [Invention 9]
Metaphenylenediamine and hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (12)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining a fluorine-containing aromatic diamine compound represented by
The method for producing a fluorine-containing aromatic diamine according to the invention 6.

で表される含フッ素芳香族ジアミンである、発明６または発明９の含フッ素芳香族ジアミンの製造方法。 [Invention 10]
The fluorine-containing aromatic diamine represented by the formula (12)

The method for producing a fluorinated aromatic diamine according to the invention 6 or 9, which is a fluorinated aromatic diamine represented by.

[Invention 11]
The method for producing a fluorine-containing aromatic diamine according to the inventions 1 to 10, which is reacted in the presence of an acid.
[Invention 12]
Aromatic diamine and
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
The first step of obtaining a fluorine-containing aromatic diamine in which a -C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
The second step of reacting the fluorine-containing aromatic diamine with the tetracarboxylic acid dianhydride to obtain a fluorine-containing aromatic polyamic acid, and
A third step of dehydrating and ring-closing the fluorinated aromatic polyamic acid to obtain a fluorinated aromatic polyimide is included.
A method for producing a fluorine-containing aromatic polyimide.

[Invention 13]
Aromatic diamine and
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
The first step of obtaining a fluorine-containing aromatic diamine in which a -C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
A second step of reacting the fluorine-containing aromatic diamine with a dicarboxylic acid or a derivative thereof, or a dicarboxylic acid dihalide to obtain a fluorine-containing aromatic polyamide.
A method for producing a fluorine-containing aromatic polyamide.

Since the method for producing an HFIP group-containing diamine of the present invention can suppress the by-product of imine, the HFIP group-containing diamine can be produced with high selectivity and yield. The method for producing an HFIP group-containing diamine, the method for producing an HFIP group-containing polyimide using the method for producing an HFIP group-containing diamine, or the method for producing an HFIP group-containing polyimide of the present invention is advantageous in industrial scale production.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and is appropriately carried out based on ordinary knowledge of those skilled in the art to the extent that the gist of the present invention is not impaired. can do.

The method for producing an HFIP group-containing diamine of the present invention is a method of reacting an aromatic diamine with HFA in HFIP to obtain an HFIP group-containing diamine.

In the method for producing an HFIP group-containing diamine of the present invention, the aromatic diamine and the HFIP group-containing diamine are, as shown below, an aromatic polycyclic compound containing two or more aromatic rings, and one aromatic. It may be an aromatic monocyclic compound containing only a ring.

（式中、Ａは、単結合、エーテル結合、スルフィド結合、ＣＯ、ＣＨ_２、ＳＯ、ＳＯ_２、Ｃ（ＣＨ_３）_２、もしくはＣ（ＣＦ_３）_２、または脂環、複素環、芳香族複素環もしくは芳香環を有する２価の基であり、Ｒ^１は、それぞれ独立に、水素原子、炭素数１～４のアルキル基、またはハロゲン原子である。）
で表される芳香族多環化合物である芳香族ジアミンと、
ＨＦＡを
ＨＦＩＰ中で反応させ、
式（２）

（式中、ＡおよびＲ^１は、式（１）における意味と同義であり、ａとｂはそれぞれ独立に０～２の整数を表し、１≦ ａ＋ｂ≦４である。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
ＨＦＩＰ基含有ジアミンの製造方法である。 1. 1. Production of HFIP group-containing diamine, which is an aromatic polycyclic compound [Production of HFIP group-containing diamine represented by the formula (2)]
The present invention has the formula (1).

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
Aromatic diamine, which is an aromatic polycyclic compound represented by
React HFA in HFIP and
Equation (2)

(In the equation, A and R ¹ have the same meaning as in the equation (1), and a and b independently represent integers of 0 to 2, and 1 ≦ a + b ≦ 4.)
Including the step of obtaining the HFIP group-containing diamine represented by.
This is a method for producing a diamine containing an HFIP group.

In the present invention, the halogen atom is any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される芳香族多環化合物である芳香族ジアミンと、
ＨＦＡを
ＨＦＩＰ中で反応させ、
式（４）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（４）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 [Production of HFIP group-containing diamine represented by the formula (4)]
Further, the present invention
Equation (3)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine, which is an aromatic polycyclic compound represented by
React HFA in HFIP and
Equation (4)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (4).

As the aromatic diamine which is an aromatic polycyclic compound represented by the formula (1), an aromatic diamine represented by the formula (3) in which _two NH groups are in the para position with respect to A can be mentioned. Further, since the HFIP group is introduced at the meta position with respect to A, the HFIP group-containing diamine represented by the formula (2) is preferably the HFIP group-containing diamine represented by the formula (4).

Among the HFIP group-containing diamines represented by the formula (4), the diamine in which ^R1 is a hydrogen atom can be exemplified below, and is commercially available from Tokyo Kasei or Wako Pure Chemical Industries, Ltd.

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される芳香族多環化合物である芳香族ジアミンと、
ＨＦＡを
ＨＦＩＰ中で反応させ、
式（６）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（６）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 [Production of HFIP group-containing diamine represented by formula (6) or formula (8)]
Further, the present invention has the formula (5).

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine, which is an aromatic polycyclic compound represented by
React HFA in HFIP and
Equation (6)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (6).

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表される芳香族ジアミンと、
ＨＦＡを、
ＨＦＩＰ中で反応させ、
式（８）

（式中、ＡおよびＲ^１は、式（１）における意味と同義である。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（８）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 Further, the present invention has the formula (7).

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine represented by
HFA,
React in HFIP,
Equation (8)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (8).

（Ｍｅはメチル基、Ｅｔはエチル基である。） As the HFIP group-containing diamine represented by the formula (6), those in which R ¹ is an alkyl group having 1 to 4 carbon atoms or a halogen atom can be exemplified below.

(Me is a methyl group and Et is an ethyl group.)

（Ｍｅはメチル基、Ｅｔはエチル基である。） As the HFIP group-containing diamine represented by the formula (8), those in which R ¹ is an alkyl group having 1 to 4 carbon atoms and a halogen atom can be exemplified below.

(Me is a methyl group and Et is an ethyl group.)

で表される芳香族ジアミンと、
ＨＦＡを、
ＨＦＩＰ中で反応させ、
式（１０）

（式中、ｃは、１～４の整数を表す。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（１０）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 2. 2. Production of HFIP group-containing diamine, which is an aromatic monocyclic compound [Production of HFIP group-containing diamine represented by the formula (10)]
The present invention has the formula (9).

Aromatic diamine represented by
HFA,
React in HFIP,
Equation (10)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (10).

[Manufacturing of HFIP group-containing diamine represented by formula (11) or formula (12)]
In the method for producing an HFIP group-containing diamine, which is an aromatic monocyclic compound of the present invention, the aromatic diamine, which is an aromatic monocyclic compound represented by the formula (9), is a para-phenylenediamine or a meta because it is easily available. It is preferable to use phenylenediamine.

（式中、ｃは、１～４の整数を表す。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（１１）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 The present invention comprises para-phenylenediamine and
HFA,
React in HFIP,
Equation (11)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (11).

（式中、ｃは、１～４の整数を表す。）
で表されるＨＦＩＰ基含有ジアミンを得る工程を含む、
式（１２）で表されるＨＦＩＰ基含有ジアミンの製造方法である。 Further, the present invention comprises meta-phenylenediamine and
HFA,
React in HFIP,
Equation (12)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining the HFIP group-containing diamine represented by.
It is a method for producing an HFIP group-containing diamine represented by the formula (12).

<HFIP group-containing diamine represented by the formula (11)>
The HFIP group-containing diamine represented by the formula (11) can be exemplified below.

In the method for producing an HFIP group-containing diamine of the present invention, the HFIP group-containing diamine represented by the formula (11) is preferably the following HFIP group-containing diamine.

<HFIP group-containing diamine represented by the formula (12)>
The HFIP group-containing diamine represented by the formula (12) can be exemplified below.

In the method for producing an HFIP group-containing diamine of the present invention, the HFIP group-containing diamine represented by the formula (12) is preferably the following HFIP group-containing diamine.

3. 3. Reaction of aromatic diamines and HFA

In the method for producing an HFIP group-containing diamine of the present invention, the procedure for reacting the aromatic diamine with HFA is not limited, but an example of a preferred embodiment will be described in detail below.

[Reactor]
Since the reactor used in the method for producing an HFIP group-containing diamine of the present invention has a boiling point of -28 ° C., it is a reactor with a cooling reflux device that prevents the outflow of HFA to the outside of the reaction system, or a sealed reactor. A sealed reactor is preferable because a reactor can be used and it is easy to handle.

In the method for producing an HFIP group-containing diamine of the present invention, when the aromatic diamine and HFA are reacted, preferably a sealed reaction vessel such as an autoclave is used, and the aromatic diamine and the HFIP, and if necessary, an acid catalyst are weighed. Place in a closed reaction vessel cooled to room temperature or below. Next, the temperature is raised to a predetermined reaction temperature so that the internal pressure of the closed reaction vessel does not exceed 0.5 MPa, and HFA is added.

[HFA]
In the method for producing an HFIP group-containing diamine of the present invention, the amount of HFA used for the reaction with the aromatic diamine as a raw material differs depending on the target HFIP group-containing diamine, and therefore the number of HFIP groups to be introduced differs. The required amount is also different.

The amount of HFA in the method for producing an HFIP group-containing diamine of the present invention is 1 equivalent or more and 3 equivalents or less, preferably 1 equivalent, with respect to the stoichiometric amount required for the reaction with the aromatic diamine as a raw material. The above is 1.5 equivalents or less. When the equivalent number of HFA is less than 1, the number of HFIP groups introduced is small, and the yield of the target HFIP group-containing diamine is low. Although the reaction proceeds even if more than 3 equivalents of HFA is used, the amino group of the raw material aromatic diamine and the target HFIP group-containing diamine react with the HFA, and the by-product of imines increases. The yield of the target HFIP group-containing diamine is lowered.

[Reaction solvent]
In the reaction according to the method for producing an HFIP group-containing diamine of the present invention, HFIP is used as a reaction solvent. Since HFIP has a high polarity, it easily dissolves aromatic diamines, and since it is weakly acidic, it also has the effect of an acid catalyst, so that the reaction can proceed rapidly without using an excessive amount of HFA. Further, since the surplus HFA can be reduced, imines that react with the raw material or the amino group of the HFIP group-containing diamine to be produced as a by-product can be suppressed, so that the HFIP group-containing diamine can be obtained with high selectivity and yield.

In the method for producing an HFIP group-containing diamine of the present invention, the amount of HFIP used is expressed as a mass ratio to the aromatic diamine as a raw material, and is preferably aromatic diamine: HFIP = 1: 0.1 to 100. , Aromatic diamine: HFIP = 1: 0.5 to 50, and particularly preferably aromatic diamine: HFIP = 1: 1 to 20. It is not necessary to use more than 100 HFIPs for 1 amount of aromatic diamines, which is economically unfavorable.

If the amount of HFIP with respect to the amount of aromatic diamine 1 is less than 0.1, HFIP cannot sufficiently dissolve the aromatic diamine, the slurry concentration becomes high, and stirring becomes difficult in the reaction, which is not preferable.

In the method for producing an HFIP group-containing diamine of the present invention, it is preferable that HFIP alone is used as the reaction solvent. Any solvent that does not inhibit the reaction (referred to as "other solvent" in this paragraph) can be appropriately mixed and used. The amount of the other solvent is preferably in the range of 20% by mass with respect to the total amount of the solvent. As an "other solvent" that does not inhibit the reaction, an aromatic hydrocarbon solvent can be mentioned. For example, benzene, toluene, xylene, ethylbenzene or mesitylene can be exemplified. Toluene or xylene is preferred.

[catalyst]
Whether or not a catalyst is used in the method for producing an HFIP group-containing diamine of the present invention depends on the type of aromatic diamine as a raw material.

As the catalyst, Bronsted acid or Lewis acid can be used without particular limitation, and may be a liquid or a solid at room temperature (20 ° C.). Examples of such an acid catalyst include liquid sulfuric acid, hydrochloric acid, paratoluene sulfonic acid, paratoluene sulfonic acid monohydrate or trifluoromethanesulfonic acid, or solid acidic ion exchange resin, acidic clay or heteropolyacid. It can be exemplified. Among these acid catalysts, p-toluenesulfonic acid monohydrate or trifluoromethanesulfonic acid is preferable because it is easily available and easy to handle.

The amount of the acid catalyst used is expressed as a molar ratio to the aromatic diamine, and the aromatic diamine: acid catalyst = 1: 0 to 0.5, preferably 1: 0.005 to 0.2, and further. It is preferably 1: 0.01 to 0.1. If the amount of the acid catalyst is small, the effect of improving the reaction rate is small, and if it is more than 0.5, it is economically unfavorable.

[Reaction temperature]
In the method for producing an HFIP group-containing diamine of the present invention, the reaction temperature for reacting an aromatic diamine with HFA to obtain an HFIP group-containing diamine is 20 ° C. or higher and 160 ° C. or lower, preferably 50 ° C. or higher. It is 140 ° C. or lower, more preferably 60 ° C. or higher and 120 ° C. or lower. If the temperature is lower than 20 ° C., the reaction rate is extremely slow, which is not a practical manufacturing method. Further, when the temperature exceeds 160 ° C., the HFA reacts with the amino group of the aromatic diamine which is the raw material or the amino group of the HFIP group-containing diamine which is the target substance, the by-product of imines increases, and the HFIP group-containing diamine The yield decreases.

[Reaction time]
In the method for producing an HFIP group-containing diamine of the present invention, the reaction time for reacting an aromatic diamine with HFA to obtain an HFIP group-containing diamine depends on the reaction temperature or the amount of HFIP as a reaction solvent. Completion of the reaction can be confirmed by monitoring the consumption of the raw material aromatic diamine.

[Purification of reactants]
In the method for producing an HFIP group-containing diamine of the present invention, the HFIP group-containing diamine can be obtained by purifying a reaction product by a known method. As the purification method, routine methods such as extraction, distillation, and crystallization can be appropriately combined. For example, HFIP and the like can be distilled off from the reaction product and then purified by crystallization to obtain an HFIP group-containing diamine. Further, if necessary, the HFIP group-containing diamine can be further purified by column chromatography or recrystallization.

[Reuse of HFIP]
The HFIP remaining after the reaction is completed can be separated and recovered from the reaction product by distillation. The recovered HFIP can be reused as a reaction solvent when reacting the aromatic diamine with HFA in the method for producing an HFIP group-containing diamine of the present invention. If necessary, the recovered HFIP may be dehydrated to remove water and reused as a reaction solvent.

[Use of HFIP group-containing diamine]
In the method for producing a HFIP group-containing diamine of the present invention, the obtained fluorine-containing aromatic diamine is reacted with a dicarboxylic acid or a tetracarboxylic acid dianhydride to synthesize high molecular weight substances such as polyamide, polyamic acid and polyimide. Can be used for.

4. Method for Producing Fluorine-Containing Aromatic Polyimide The method for producing a fluorine-containing aromatic polyimide of the present invention (hereinafter, may be referred to as HFIP group-containing polyimide) is as follows.
Aromatic diamine and
HFA,
React in HFIP,
The first step of obtaining a fluorine-containing aromatic diamine (HFIP group-containing diamine) in which an HFIP group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
The second step of reacting the HFIP group-containing diamine with the tetracarboxylic acid dianhydride to obtain a fluorine-containing aromatic polyamic acid (hereinafter, may be referred to as HFIP group-containing polyamic acid).
The present invention comprises a third step of dehydrating and closing the HFIP group-containing polyamic acid to obtain a fluorine-containing aromatic polyimide (hereinafter, may be referred to as HFIP group-containing polyimide).

In the method for producing an HFIP group-containing polyimide of the present invention, the HFIP group-containing diamine used may contain two or more aromatic rings or only one aromatic ring, as shown below.

（式中、Ａは、単結合、エーテル結合、スルフィド結合、ＣＯ、ＣＨ_２、ＳＯ、ＳＯ_２、Ｃ（ＣＨ_３）_２、もしくはＣ（ＣＦ_３）_２、または脂環、複素環、芳香族複素環もしくは芳香環を有する２価の基であり、Ｒ^１は、それぞれ独立に、水素原子、炭素数１～４のアルキル基、またはハロゲン原子である。ａとｂはそれぞれ独立に０～２の整数を表し、１≦ ａ＋ｂ≦４である。）
式（１３）

（式中、Ｒ^２は脂環、複素環、芳香環、または直鎖状もしくは分枝鎖状の脂肪族炭化水素基らなる群から選ばれた少なくとも一種を含む４価の有機基であり、水素原子の一部がアルキル基、フルオロアルキル基、カルボキシル基、ヒドロキシ基、シアノ基、またはハロゲン基で置換されてもよい。）
式（１４）

（式中、ＡおよびＲ^１は、式（１）における意味と同義であり、ａとｂは、それぞれ独立に、０～２の整数であり、１≦ａ＋ｂ≦４である。Ｒ^２は、式（１３）における意味と同義である。）
式（１５）

（式中、ＡおよびＲ^１は、式（１）における意味と同義であり、ａとｂは、それぞれ独立に、０～２の整数であり、１≦ａ＋ｂ≦４である。Ｒ^２は、式（１３）における意味と同義である。） 4-1.2 Method for Producing HFIP Group-Containing Polyimide Using HFIP Group-Containing Diamine Containing Two or More Aromatic Rings The HFIP group-containing polyimide using HFIP group-containing diamine containing two or more aromatic rings of the present invention. The manufacturing method is
The aromatic diamine represented by the following formula (1) and
HFA,
React in HFIP,
The first step of obtaining an HFIP group-containing diamine represented by the formula (2) in which an HFIP group is bonded to an aromatic ring having an amino group in the aromatic diamine represented by the formula (1) as a starting material.
The HFIP group-containing diamine represented by the formula (2) is reacted with the tetracarboxylic acid dianhydride represented by the following formula (13) to contain a repeating unit represented by the formula (14). The second step of obtaining the contained polyamic acid and
The third step of dehydrating and ring-closing the HFIP group-containing polyamic acid containing the repeating unit represented by the formula (14) to obtain the HFIP group-containing polyimide containing the repeating unit represented by the formula (15) is included. ..
Equation (1), Equation (2)

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is an independently hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. A and b are independently 0 to 2 respectively. Represents an integer of 1 ≦ a + b ≦ 4.)
Equation (13)

(In the formula, R ² is a tetravalent organic group containing at least one selected from the group consisting of alicyclic, heterocyclic, aromatic rings, or linear or branched aliphatic hydrocarbon groups. A part of the hydrogen atom may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or a halogen group.)
Equation (14)

(In the equation, A and R ¹ have the same meaning as in the equation (1), a and b are independently integers of 0 to ² , and 1 ≦ a + b ≦ 4. It is synonymous with the meaning in equation (13).)
Equation (15)

(In the equation, A and R ¹ have the same meaning as in the equation (1), a and b are independently integers of 0 to ² , and 1 ≦ a + b ≦ 4. It is synonymous with the meaning in equation (13).)

（ｃは、１～４の整数を表す。）
式（１３）

（式中、Ｒ^２は脂環、複素環、芳香環、または直鎖状もしくは分枝鎖状の脂肪族炭化水素基らなる群から選ばれた少なくとも一種を含む４価の有機基であり、水素原子の一部がアルキル基、フルオロアルキル基、カルボキシル基、ヒドロキシ基、シアノ基、またはハロゲン基で置換されてもよい。）
式（１６）

（式中、Ｒ^２は、式（１３）における意味と同義であり、ｃは、１～４の整数を表す。）
式（１７）

（式中、Ｒ^２は、式（１３）における意味と同義であり、ｃは、１～４の整数を表す。） 4-2. Method for Producing HFIP Group-Containing Polyimide Using HFIP Group-Containing Diamine Containing Only a Single Ring Aromatic Ring The method for producing an HFIP group-containing polyimide using an HFIP group-containing diamine containing only a monocyclic aromatic ring according to the present invention.
The aromatic diamine represented by the following formula (9) and
HFA,
React in HFIP,
The first step of obtaining an HFIP group-containing diamine represented by the formula (10) in which an HFIP group is bonded to an aromatic ring having an amino group in the aromatic diamine represented by the formula (9) as a starting material.
The HFIP group-containing diamine represented by the formula (10) is reacted with the tetracarboxylic acid dianhydride represented by the following formula (13) to contain HFIP containing a repeating unit represented by the formula (16). The second step of obtaining polyamic acid and
The third step of dehydrating and ring-closing the HFIP group-containing polyamic acid represented by the formula (16) to obtain an HFIP group-containing polyimide containing a repeating unit represented by the formula (17) is included.
Equation (9), Equation (10)

(C represents an integer of 1 to 4.)
Equation (13)

(In the formula, R ² is a tetravalent organic group containing at least one selected from the group consisting of alicyclic, heterocyclic, aromatic rings, or linear or branched aliphatic hydrocarbon groups. A part of the hydrogen atom may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or a halogen group.)
Equation (16)

(In the equation, R ² has the same meaning as in the equation (13), and c represents an integer of 1 to 4.)
Equation (17)

(In the equation, R ² has the same meaning as in the equation (13), and c represents an integer of 1 to 4.)

4-3. Tetracarboxylic acid dianhydride represented by formula (13) The tetracarboxylic acid dianhydride used in the method for producing an HFIP group-containing polyimide of the present invention is generally known as a polyamic acid or a raw material compound for polyimide. If it is a thing, it can be used without any particular limitation.

Examples of such tetracarboxylic acid dianhydride include benzenetetracarboxylic acid dianhydride (pyromellitic acid dianhydride) (hereinafter, may be referred to as PMDA), trifluoromethylbenzenetetracarboxylic acid dianhydride, and bistri. Fluoromethylbenzenetetracarboxylic acid dianhydride, difluorobenzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride (hereinafter, may be referred to as BPDA), terphenyltetracarboxylic acid. Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ketone acid dianhydride (hereinafter, may be referred to as BTDA), oxydiphthalic acid dianhydride (hereinafter, abbreviated as ODPA), bicyclo (hereinafter, abbreviated as ODPA). 2,2,2) Oct-7-en-2,3,5,6-tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropaneic acid dianhydride (hereinafter) , 6FDA), 2,3,4,5-thiophenetetracarboxylic hydride, 2,2', 5,5', 6,6'-hexafluoro-3,3', 4 , 4'-biphenyltetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride (hereinafter sometimes referred to as DSDA) or 3,4,9,10-perylenetetracarboxylic acid. (2) Anhydride can be exemplified. Two or more of these tetracarboxylic acid dianhydrides may be used in combination.

In the method for producing the HFIP group-containing polyimide of the present invention, PMDA, BPDA, 6FDA, BTDA, ODPA, and DSDA are particularly used because they are easily available, have excellent heat resistance, and are easily soluble in a solvent. Is preferable.

4-4. The first step in the method for producing the HFIP group-containing polyimide of the present invention The first step in the method for producing the HFIP group-containing polyimide of the present invention is
Aromatic diamine and
HFA,
React in HFIP,
This is a step of obtaining a fluorine-containing aromatic diamine (HFIP group-containing diamine) in which an HFIP group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
This step can be performed in the same manner as the above-mentioned method for producing a HFIP group-containing diamine of the present invention.

4-5. The second step in the method for producing the HFIP group-containing polyimide of the present invention In the second step in the method for producing the HFIP group-containing polyimide of the present invention, the HFIP group-containing diamine obtained in the first step and the tetracarboxylic acid di This is a step of reacting an anhydride to obtain an HFIP group-containing polyamic acid. The second step can be performed based on the method described in Patent Documents 5 to 7.

In the second step in the method for producing an HFIP group-containing polyimide of the present invention, the ratio of the tetracarboxylic acid dianhydride to the HFIP group-containing diamine used is 0.9 mol or more with respect to 1 mol of the tetracarboxylic acid dianhydride. , 1.1 mol or less, preferably 0.95 mol or more and 1.05 mol or less, more preferably 0.98 mol or more and 1.03 mol or less. If it is out of this range, the physical properties of the obtained HFIP group-containing polyimide may deteriorate.

The method and reaction conditions of the polymerization reaction for obtaining the HFIP group-containing polyamic acid in the second step of the method for producing the HFIP group-containing polyimide of the present invention are not particularly limited. For example, a method in which an HFIP group-containing diamine and a tetracarboxylic acid dianhydride are mutually melted (melted) at 150 ° C. or higher and lower than 250 ° C. and reacted without a solvent, or at a high temperature (preferably 150 ° C. or higher) in an organic solvent. Examples thereof include a method of reacting in an organic solvent at −20 ° C. to 80 ° C. and a method of reacting in an organic solvent.

Examples of the organic solvent used in the method of reacting in the organic solvent at a high temperature (preferably 150 ° C. or higher) and the method of reacting in the organic solvent of −20 ° C. to 80 ° C. include the HFIP group-containing diamine and tetracarboxylic acid dianhydride. It suffices if the substance is dissolved, and examples thereof include an amide solvent, an aromatic solvent, a halogen solvent, and a lactone solvent. A polyamic acid having a high degree of polymerization can be obtained by carrying out the reaction in the coexistence of an acid receptor such as pyridine or triethylamine together with the above-mentioned amide solvent.

Examples of such an amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, N-methyl-2-pyrrolidone and the like. can.

Examples of the aromatic solvent include benzene, toluene, xylene, anisole, diphenyl ether, nitrobenzene and benzonitrile.
Examples of the halogen-based solvent include chloroform, dichloromethane, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.

Examples of the lactone-based solvent include γ-butyl lactone, γ-valero lactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyl lactone and the like.

Further, two or more of these organic solvents may be used in combination.

In the second step of the method for producing an HFIP group-containing polyimide of the present invention, in addition to the HFIP group-containing diamine obtained in the first step, a diamine having no HFIP group, a polyamic acid using a dihydroxyamine in combination, or the like Other diamines may be added and reacted with the tetracarboxylic acid dianhydride to give an HFIP group-containing polyamic.

Other diamines include 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3'-bistrifluoromethyl-4,4'-diaminobiphenyl, 2,2'-bistrifluoromethyl-. 4,4'-Diaminobiphenyl, 3,3'-bistrifluoromethyl-5,5'-diaminobiphenyl, bis (trifluoromethyl) -4,4'-diaminobiphenyl, bis (alkyl fluorinated) -4,4 '-Diaminobiphenyl, dichloro-4,4'-diaminobiphenyl, dibromo-4,4'-diaminobiphenyl, bis (fluorinated alkoxy) -4,4'-diaminobiphenyl, diphenyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminotetrafluorophenoxy) tetrafluorobenzene, 4,4'-bis (4-aminotetrafluorophenoxy) octafluorobiphenyl, 4,4'-binaphthylamine, o-phenylenediamine, m -Phenylenediamine, p-Phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminojurene, 1,4-xylylenediamine, dimethyl-4, 4'-diaminobiphenyl, dialkyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, dimethoxy-4, 4'-diaminobiphenyl, diethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-dimethyl-diaminodiphenylmethane, 3,3'-diethyl-diaminodiphenylmethane, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1 , 3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) Biphenyl Enyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2, 2-Bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy)) Phenyl) Hexafluoropropane, 2,2-bis (4- (4-amino-2-trifluoromethylphenoxy) phenyl) Hexafluoropropane, 2,2-bis (4- (3-amino-5-trifluoromethyl) Phenoxy) Phenyl) Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-) Hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 4,4'-bis (4-aminophenoxy) octafluorobiphenyl or 4,4'-diaminobenzanilide Can be exemplified. Two or more kinds of diamines having no HFIP group may be used in combination.

4-5. The third step in the method for producing the HFIP group-containing polyimide of the present invention In the third step in the method for producing the HFIP group-containing polyimide of the present invention, the HFIP group-containing polyamic acid obtained in the second step is dehydrated and closed. This is a step of obtaining a fluorine-containing aromatic polyimide. The third step can be performed based on the method described in Patent Documents 5 to 7.

In the third step of the method for producing the HFIP group-containing polyimide of the present invention, the HFIP group-containing polyamic acid obtained in the second step is dehydrated and closed to form an imide ring by heating or reaction with a dehydration reagent. An HFIP group-containing polyimide can be obtained.

In the method for producing an HFIP group-containing polyimide of the present invention, a second step, a step of reacting the above-mentioned HFIP group-containing diamine with the tetracarboxylic acid dianhydride by heating to obtain an HFIP group-containing polyamic acid. The third step, that is, the step of dehydrating and closing the ring in the HFIP group-containing polyamic acid compound by heating to obtain the HFIP group-containing polyimide may be carried out at the same time.

[Imidization by heat dehydration ring closure]
When the HFIP group-containing polyamic acid compound is dehydrated and closed by heating to perform imidization, an imide ring is formed at a temperature of 80 ° C. or higher and 350 ° C. or lower, and an HFIP group-containing polyimide can be obtained. It is preferably 150 ° C. or higher, more preferably 200 ° C. or higher. When the temperature is less than 80 ° C., dehydration ring closure does not proceed completely and the imidization rate is insufficient, and when the HFIP group-containing polyimide is used as a coating film, the film strength is impaired or the water absorption becomes high. There is a risk. On the other hand, if the temperature exceeds 350 ° C., a part of the polyimide may be thermally decomposed, and the film strength may be impaired or colored when the polyimide is used as a coating film.

[Imidization by dehydration ring closure using dehydration reagent]
When dehydration ring closure is performed in the HFIP group-containing polyamic acid compound using a dehydration reagent, acetic anhydride and a base such as pyridine or triethylamine are added as the dehydration reagent, and dehydration is performed in the HFIP group-containing polyamic acid compound. By doing so, it is also possible to obtain an HFIP group-containing polyimide. At this time, the amount of the dehydration reagent added is preferably 2 mol or more and 10 mol or less, and the amount of the base added is preferably 2 mol or more and 10 mol or less with respect to 1 mol of the HFIP group-containing polyamic acid.

4-6. HFIP group-containing polyimide The HFIP group-containing polyimide containing the repeating unit represented by the formula (15) or the formula (17) obtained by the method for producing the HFIP group-containing polyimide of the present invention has a weight average molecular weight (Mw) in terms of polystyrene. Is preferably 10,000 or more and 500,000 or less. When Mw is less than 10000, the strength of the HFIP group-containing polyimide is low and it is difficult to form a self-standing film, and when it is larger than 500,000, the HFIP group-containing polyimide has low solubility in an organic solvent. Particularly preferably, it is 50,000 or more and 150,000 or less.

The HFIP group-containing polyimide obtained by the method for producing an HFIP group-containing polyimide of the present invention can be used in a varnish state, a powder state, a film state, and a solid state dissolved in an organic solvent. At that time, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitive agent, a photopolymerization initiator or a sensitizer may be added to the obtained HFIP group-containing polyimide, if necessary. .. When used in varnish, it can be applied on glass, silicon wafers, metals, metal oxides, ceramics, resins, etc. by known methods such as spin coating, spray coating, flow coating, impregnation coating, and brush coating. ..

5. Method for Producing Fluorine-Containing Aromatic Polyamide The method for producing a fluorine-containing aromatic polyamide (hereinafter, may be referred to as HFIP group-containing polyamide) of the present invention is as follows.
Aromatic diamine and
HFA,
React in HFIP,
The first step of obtaining a fluorine-containing aromatic diamine (HFIP group-containing diamine) in which an HFIP group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
The present invention comprises a second step of reacting the HFIP group-containing diamine with a dicarboxylic acid or a derivative thereof, or a dicarboxylic acid dihalide to obtain an HFIP-containing polyamide.
In the method for producing an HFIP group-containing polyamide of the present invention, the HFIP group-containing diamine used may contain two or more aromatic rings or only one aromatic ring as shown below.

（式中、Ａは、単結合、エーテル結合、スルフィド結合、ＣＯ、ＣＨ_２、ＳＯ、ＳＯ_２、Ｃ（ＣＨ_３）_２、もしくはＣ（ＣＦ_３）_２、または脂環、複素環、芳香族複素環もしくは芳香環を有する２価の基であり、Ｒ^１は、それぞれ独立に、水素原子、炭素数１～４のアルキル基、またはハロゲン原子である。ａとｂはそれぞれ独立に０～２の整数を表し、１≦ ａ＋ｂ≦４である。）
式（１８）

（式中、Ｒ^３は脂環、複素環、芳香環または直鎖状もしくは分枝鎖状脂肪族炭化水素基からなる群から選ばれた少なくとも一種を含む２価の有機基であり、フッ素、塩素、酸素、硫黄、窒素などを含有してもよく、さらには水素原子の一部がアルキル基、フルオロアルキル基、カルボキシル基、ヒドロキシ基、シアノ基で置換されてもよい。Ｒ^４は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基またはベンジル基から選ばれた少なくとも一種の基である。）
式（１９）

（式中、Ｒ^３は式（１８）における意味と同義であり、Ｘはハロゲン原子である。）
式（２０）

（式中、ＡおよびＲ^１は、式（２）における意味と同義であり、ａとｂは、それぞれ独立に、０～２の整数であり、１≦ａ＋ｂ≦４である。Ｒ^３は式（１８）における意味と同義である。） 5-1.2 Method for Producing HFIP Group-Containing Polyamide Using HFIP Group-Containing Diamines Containing Two or More Aromatic Rings The HFIP group-containing polyamide using the HFIP group-containing diamine containing two or more aromatic rings of the present invention. The manufacturing method is
The aromatic diamine represented by the following formula (1) and
HFA,
React in HFIP,
The first step of obtaining an HFIP group-containing diamine represented by the formula (2) in which an HFIP group is bonded to an aromatic ring having an amino group in the aromatic diamine represented by the formula (1) as a starting material.
The HFIP group-containing diamine represented by the formula (2) is reacted with a dicarboxylic acid or a derivative thereof represented by the following formula (18) or a dicarboxylic acid halide represented by the formula (19) to react with the formula (1). A second step of obtaining an HFIP group-containing polyamide containing the repeating unit represented by 20) is included.
Equation (1), Equation (2)

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is an independently hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. A and b are independently 0 to 2 respectively. Represents an integer of 1 ≦ a + b ≦ 4.)
Equation (18)

(In the formula, R ³ is a divalent organic group containing at least one selected from the group consisting of alicyclic, heterocyclic, aromatic rings or linear or branched aliphatic hydrocarbon groups, and is a divalent organic group containing fluorine. It may contain chlorine, oxygen, sulfur, nitrogen and the like, and a part of the hydrogen atom may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, etc. R ⁴ is each substituted. Independently, it is at least one group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a benzyl group.)
Equation (19)

(In the formula, R ³ has the same meaning as in the formula (18), and X is a halogen atom.)
Equation (20)

(In the equation, A and R ¹ have the same meaning as in the equation (2), a and b are independently integers of 0 to 2, and 1 ≦ a + b ≦ 4, respectively. R ³ is the formula. It is synonymous with the meaning in (18).)

（ｃは、１～４の整数を表す。）
式（１８）

（式中、Ｒ^３は脂環、複素環、芳香環または直鎖状もしくは分枝鎖状脂肪族炭化水素基からなる群から選ばれた少なくとも一種を含む２価の有機基であり、フッ素、塩素、酸素、硫黄、窒素などを含有してもよく、さらには水素原子の一部がアルキル基、フルオロアルキル基、カルボキシル基、ヒドロキシ基、シアノ基で置換されてもよい。Ｒ^４は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基またはベンジル基から選ばれた少なくとも一種の基である。）
式（１９）

（式中、Ｒ^３は式（１８）における意味と同義であり、Ｘはハロゲン原子である。）
式（２１）

（式中、Ｒ^３は式（１８）における意味と同義であり、ｃは、１～４の整数を表す。） 5-2. Method for Producing HFIP Group-Containing Polyamide Using HFIP Group-Containing Diamine Containing Only a Single Ring Aromatic Ring The method for producing an HFIP group-containing polyamide using an HFIP group-containing diamine containing only a monocyclic aromatic ring according to the present invention.
The aromatic diamine represented by the following formula (9) and
HFA,
React in HFIP,
The first step of obtaining an HFIP group-containing diamine represented by the formula (10) in which an HFIP group is bonded to an aromatic ring having an amino group in the aromatic diamine represented by the formula (9) as a starting material.
A dicarboxylic acid represented by the following formula (18) or a derivative thereof, or a dicarboxylic acid halide represented by the formula (19) is reacted to obtain an HFIP group-containing polyamide containing a repeating unit represented by the formula (21). Includes a second step of obtaining.
Equation (9), Equation (10)

(C represents an integer of 1 to 4.)
Equation (18)

(In the formula, R ³ is a divalent organic group containing at least one selected from the group consisting of alicyclic, heterocyclic, aromatic rings or linear or branched aliphatic hydrocarbon groups, and is a divalent organic group containing fluorine. It may contain chlorine, oxygen, sulfur, nitrogen and the like, and a part of the hydrogen atom may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, etc. R ⁴ is each substituted. Independently, it is at least one group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a benzyl group.)
Equation (19)

(In the formula, R ³ has the same meaning as in the formula (18), and X is a halogen atom.)
Equation (21)

(In the equation, R ³ has the same meaning as in the equation (18), and c represents an integer of 1 to 4.)

5-3. The dicarboxylic acid represented by the formula (18) or a derivative thereof The dicarboxylic acid represented by the formula (18) or a derivative thereof used in the method for producing a HFIP group-containing polyamide of the present invention is generally known as a raw material compound for a polyamide. It can be used without any particular restrictions as long as it is a product.

Examples of the dicarboxylic acid include an aliphatic carboxylic acid and an aromatic dicarboxylic acid. The dicarboxylic acid derivative represented by the formula (18) is obtained by protecting the carboxyl groups of these carboxylic acids with _R4 excluding hydrogen atoms.

Examples of the aliphatic carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-dicarboxybiphenyl, 3,3'-dicarboxybiphenyl, 3,3'-dicarboxydiphenyl ether, and 3,4'-dicarboxyl. Diphenyl ether, 4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenylmethane, 3,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenyldifluoromethane, 3 , 4'-dicarboxydiphenyldifluoromethane, 4,4'-dicarboxydiphenyldifluoromethane, 3,3'-dicarboxydiphenylsulfone, 3,4'-dicarboxydiphenylsulfone, 4,4'-dicarboxydiphenylsulfone , 3,3'-dicarboxydiphenylsulfide, 3,4'-dicarboxydiphenylsulfide, 4,4'-dicarboxydiphenylsulfide, 3,3'-dicarboxydiphenylketone, 3,4'-dicarboxydiphenylketone , 4,4'-Dicarboxydiphenylketone, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (3,4'-dicarboxyphenyl) propane, 2,2-bis (4-carboxy) Phenyl) propane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2-bis (3,4'-dicarboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexa Fluoropropane, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 3,3'-(1, 4-Phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4'-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4'-(1,4-phenylenebis) (1-Methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) propane, 2,2 -Bis (4- (3-carboxyphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxyphenoxy) phenyl ) Sulfate, bis (4- (4-carboxyphenoxy) phenyl) sulfide, bis (4- (3-carboxyphenoxy) phenyl) sulfone or bis (4- (4-carboxyphenoxy) phenyl) sulfone, perfluorononenyloxy Group-containing dicarboxylic acids 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid, 2- (perfluorononenyloxy) terephthalic acid or 4-methoxy-5-( Perfluorononenyloxy) Isophthalic acid, a dicarboxylic acid containing a perfluorohexenyloxy group, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) ) Telephthalic acid or 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid, 2,2'-ditrifluoromethyl-4,4'-dicarboxybiphenyl can be exemplified.

5-4. Dicarboxylic acid dihalide represented by the formula (19) The dicarboxylic acid dihalide represented by the formula (19) is the dicarboxylic acid represented by the formula (18) in which the carboxyl group of the above carboxylic acid is replaced with a halogen atom.
Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

5-5. The first step in the method for producing the HFIP group-containing polyamide of the present invention The first step in the method for producing the HFIP group-containing polyamide of the present invention is
Aromatic diamine and
HFA,
React in HFIP,
This is a step of obtaining a fluorine-containing aromatic diamine (HFIP group-containing diamine) in which an HFIP group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
This step can be performed in the same manner as the above-mentioned method for producing a HFIP group-containing diamine of the present invention.

5-6. The second step in the method for producing the HFIP group-containing polyamide of the present invention The second step in the method for producing the HFIP group-containing polyamide of the present invention is the HFIP group-containing diamine obtained in the first step and a dicarboxylic acid or a dicarboxylic acid thereof. This is a step of reacting a derivative or a dicarboxylic acid dihalide to obtain an HFIP group-containing polyamide. The second step can be performed based on the method described in Patent Documents 5 to 7.

In the second step in the method for producing an HFIP group-containing polyamide of the present invention, the ratio of the dicarboxylic acid or its derivative to the diamine component is 0.9 to 1 mol with respect to 1 mol of the dicarboxylic acid or its derivative or the dicarboxylic acid dihalide. It is 1.1 mol, preferably 0.95 to 1.05 mol, and more preferably 0.98 to 1.03 mol. If it is out of this range, the physical properties of the obtained HFIP group-containing polyamide may deteriorate.

The method and reaction conditions of the polymerization reaction for obtaining the HFIP group-containing polyamide in the second step of the method for producing the HFIP group-containing polyamide of the present invention are not particularly limited. For example, a method in which the diamine component and the dicarboxylic acid or a derivative thereof or a dicarboxylic acid dihalide are mutually melted (melted) at 150 ° C. or higher and lower than 250 ° C. and reacted without a solvent, or an organic substance at −20 ° C. to 80 ° C. A method of reacting in a solvent can be exemplified.

As the organic solvent used in the method of reacting in the organic solvent of −20 ° C. to 80 ° C. in the organic solvent, the HFIP group-containing diamine and the dicarboxylic acid or its derivative, or the dicarboxylic acid dihalide can be used as the organic solvent. Both may be dissolved, and examples thereof include an amide-based solvent, an aromatic solvent, a halogen-based solvent, and a lactone-based solvent.

When obtaining the HFIP group-containing polyamide in the second step of the method for producing the HFIP group-containing polyamide of the present invention, an acid acceptor such as pyridine or triethylamine is allowed to coexist with these organic solvents to carry out the reaction. It is preferable to do so. In particular, when an amide-based solvent is used, these solvents themselves become acid receptors, and a high-polymerization degree HFIP group-containing polyamide can be obtained.

Examples of such an amide-based solvent include N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric acid triamide or N-methyl-2-, and pyrrolidone.

Examples of the aromatic solvent include benzene, toluene, xylene, anisole, diphenyl ether, nitrobenzene, and benzonitrile.

Examples of the halogen-based solvent include chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane.
Examples of the lactone-based solvent include γ-butyl lactone, γ-valero lactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyl lactone and the like.

Further, two or more of these organic solvents may be used in combination.

In the second step in the method for producing an HFIP group-containing polyamide of the present invention, in addition to the HFIP group-containing diamine obtained in the first step, a diamine having no HFIP group, a polyamic acid in which a dihydroxyamine is used in combination, etc. Other diamines may be added and reacted with a dicarboxylic acid or a derivative thereof, or a dicarboxylic acid dihalide to obtain an HFIP group-containing polyamide.

As the diamine used in the second step in the method for producing the HFIP group-containing polyamide of the present invention, the same diamine used in the second step in the method for producing the HFIP group-containing polyimide of the present invention can be used. The same applies to the fact that more than seeds can be used together.

5-6. HFIP group-containing polyamide The HFIP group-containing polyamide obtained by the method for producing an HFIP group-containing polyamide of the present invention and containing a repeating unit represented by the formula (20) or the formula (21) has a weight average molecular weight (Mw) in terms of polystyrene. ) Is preferably 10,000 or more and 500,000 or less. When Mw is less than 10,000, the strength of the obtained HFIP group-containing polyamide is low and it is difficult to form a self-supporting film, and when it is more than 500,000, the obtained HFIP group-containing polyamide has low solubility in an organic solvent. .. Particularly preferably, it is 50,000 or more and 150,000 or less.

（式中、ＡおよびＲ^１は、式（４）における意味と同義であり、Ｒ^３は式（１８）における意味と同義である。）
式（２３）

（式中、ＡおよびＲ^１は、式（４）における意味と同義であり、Ｒ^３は式（１８）における意味と同義である。） 6. HFIP group-containing polymer and method for producing the same By cyclizing the contained polyamide containing the repeating unit represented by the following formula (22) obtained by the method for producing the HFIP group-containing polyamide of the present invention, the formula ( An HFIP group-containing polymer containing the repeating unit represented by 23) can be obtained. The cyclization reaction can be carried out by heating, or can be carried out by a method of promoting dehydration such as adding an acid catalyst and heating.
Equation (22)

(In the formula, A and R ¹ are synonymous with the meaning in the formula (4), and R ³ is synonymous with the meaning in the formula (18).)
Equation (23)

(In the formula, A and R ¹ are synonymous with the meaning in the formula (4), and R ³ is synonymous with the meaning in the formula (18).)

（式中、Ｒ^３は式（１８）における意味と同義である。）
式（２５）

（式中、Ｒ^３は式（１８）における意味と同義である。） Further, by cyclizing the contained polyamide containing the repeating unit represented by the following formula (24) obtained by the method for producing the HFIP group-containing polyamide of the present invention, the repetition represented by the formula (25). An HFIP group-containing polymer containing a unit can be obtained. The cyclization reaction can be carried out by heating, or can be carried out by a method of promoting dehydration such as adding an acid catalyst and heating.
Equation (24)

(In the formula, R ³ has the same meaning as in the formula (18).)
Equation (25)

(In the formula, R ³ has the same meaning as in the formula (18).)

As described in Patent Documents 5 to 7, the HFIP group-containing polyamide containing the repeating unit represented by the formula (22) or the formula (24) is dehydrated in the compound by heat treatment or reaction with a dehydration reagent. , A ring structure is formed, and an HFIP group-containing polymer containing a repeating unit represented by the formula (23) or the formula (25) can be synthesized. When dehydrated and cyclized by heat treatment, the HFIP group-containing polymer is cyclized at a reaction temperature of 250 ° C. or higher and 400 ° C. or lower and contains a repeating unit represented by the formula (23) or the formula (25). Can be synthesized. More preferably, it is 300 ° C. or higher and 380 ° C. or lower. If the reaction temperature is lower than 250 ° C., cyclization does not proceed sufficiently, and when the HFIP group-containing polymer is used as a coating film, the film strength may be impaired or the water absorption may be increased. On the other hand, if the reaction temperature exceeds 400 ° C., a part of the HFIP group-containing polymer may be thermally decomposed, and the film strength may be impaired or colored when the HFIP group-containing polymer is used as a coating film. There is. When performing dehydration cyclization using a dehydration reagent, acetic anhydride is added as the dehydration reagent, a base such as pyridine or triethylamine is further added, the polyamide is reacted with the polyamide, and dehydration cyclization is performed to obtain the HFIP group-containing weight. It is also possible to synthesize coalescence.

The HFIP group-containing polymer containing the repeating unit represented by the formula (23) or the formula (25) obtained by the above method has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 or more and 500,000 or less. preferable. When Mw is less than 10,000, the strength of the HFIP group-containing polymer is low and it is difficult to form a self-standing film, and when it is more than 500,000, the HFIP group-containing polymer is inferior in solubility in an organic solvent. Particularly preferably, it is 50,000 or more and 150,000 or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

1. 1. Synthesis of HFIP group-containing diamine, which is an aromatic bicyclic compound 1-1. Synthesis Example 1 of HFIP group-containing diamine having a diphenyl skeleton
<Synthesis of 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine using HFIP as a solvent>
In a 1 L stainless steel pressure resistant reactor equipped with a pressure gauge, a thermometer and a stirrer, 80.0 g (0.38 mol) of metatridin as a raw material and 400 g of HFIP as a reaction solvent were placed, and the inside of the reactor was filled with nitrogen. After the substitution, the mixture was heated with an oil bath, and when the internal temperature reached 80 ° C., 156 g (0.94 mol, 2.5 equivalents) of HFA was added, and the reaction was carried out at 80 ° C. for 7 hours.

After completion of the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. As a result, each of them was expressed in area% and was the target product, 5,5'-bis (1-hydroxy-). 1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine was 97.6%, and the total of imines produced as by-products was 2.4%.

After completion of the reaction, the gas was cooled to room temperature (20 ° C.), the reactor was opened, and the purged gas was recovered in a glass trap in a dry ice acetone bath. Next, 600 g of toluene was placed in the reactor, and HFIP, which was a reaction solvent, was distilled off under normal pressure while heating with an oil bath, and 334 g was recovered. When the composition of the recovered HFIP was measured by gas chromatography, HFIP was 99.1% and toluene was 0.9%.

300 g of toluene was placed in the reactor, heating was continued, and the mixture was maintained for 2 hours when the internal temperature reached 110 ° C. Next, the reactor was cooled to 10 ° C., crystals of the reactants were precipitated to form a slurry, and the mixture was filtered off by a centrifuge. The obtained powder was dried under reduced pressure at 60 ° C. and 6 kPa for 2 hours to obtain the desired 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2, A white powder of 2'-dimethylbenzidine was obtained in 199 g (0.37 mol) with a yield of 96.8%. The NMR measurement data of the target product is shown below.

^{1 1} H-NMR (DMSO-d6): δ9.27 (brs, 2H), 6.80 (s, 2H), 6.65 (s, 2H), 5.54 (brs, 4H), 1.88 ( s, 6H). ¹⁹
F-NMR (DMSO-d6): δ-72.78 (s).

Example 2
<Reuse of HFIP>
In Example 1, 66 g of unused HFIP was added to 334 g of HFIP recovered after the reaction, and 400 g of HFIP was used in the same manner as in Example 1, and the same reaction as in Example 1 was carried out in the same procedure. After reacting at 80 ° C. for 7 hours, the reaction solution was sampled, and the composition (selectivity) of the reaction product was measured by gas chromatography. Bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine was 97.7%, by-product imines were 2.3%, and the procedure was carried out. It was equivalent to the result of Example 1.

Comparative Example 1
<Synthesis of 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine using ethanol as a solvent>

A stainless steel pressure reactor with an internal volume of 300 mL equipped with a pressure gauge, a thermometer and a stirrer, 50.0 g (0.24 mol) of metatridin as a raw material, 100 g of ethanol as a reaction solvent, and 1 water of paratoluenesulfonic acid as a catalyst. Add 2.02 g (0.012 mol) of Japanese product, replace the inside of the reactor with nitrogen, heat with an oil bath, and when the internal temperature reaches 110 ° C, HFA, 99.6 g (0.60 mol, 2.5 equivalents) was added, and the reaction was carried out at 110 ° C. for 24 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled, and the composition (selectivity) of the reaction product was measured by gas chromatography. 5,5'-Bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine is 10.6%, hexafluoroisopropanol group is one The introduced 5- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine was 63.8%, and the unreacted raw material metatridin was 23. .1% and others were 2.5%.

Comparative Example 2
<Synthesis of 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine using acetonitrile as a solvent>

In a stainless steel pressure reactor with an internal volume of 300 mL equipped with a pressure gauge, a thermometer and a stirrer, 25.0 g (0.12 mol) of metatridin as a raw material, 180 g of acetonitrile as a reaction solvent, and 1 water of paratoluenesulfonic acid as a catalyst. Add 1.01 g (0.006 mol) of Japanese product, replace the inside of the reactor with nitrogen, heat with an oil bath, and when the internal temperature reaches 80 ° C, HFA, 49.0 g (0.30 mol, 2.7 equivalents) was added, and the reaction was carried out at 80 ° C. for 7 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled, and the composition (selectivity) of the reaction product was measured by gas chromatography. 5,5'-Bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine is 0.4%, hexafluoroisopropanol group is one The introduced 5- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine was 18.1%, and the unreacted raw material metatridin was 23. It was 0.1% and 58.4% of imines produced as by-products.

Comparative Example 3
<Synthesis of 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2'-dimethylbenzidine using HFA trihydrate as a raw material>
In a stainless steel pressure reactor with an internal volume of 300 mL equipped with a pressure gauge, a thermometer and a stirrer, 42.4 g (0.20 mol) of metatridin as a raw material, 220 g (1.00 mol) of HFA trihydrate, as a catalyst. 1.90 g (0.01 mol) of paratoluenesulfonic acid monohydrate was added, the inside of the reactor was replaced with nitrogen, the reactor was heated to 135 ° C by heating with an oil bath, and then 22 at 135 ° C. Time, reaction was done.

After cooling the reactor to room temperature (20 ° C.) to complete the reaction, the reactor was unsealed, and the reaction product was transferred to a centrifuge and filtered to obtain a powder. The recovered powder was washed with diisopropyl ether and dried under reduced pressure to obtain 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -2,2. A white powder of'-dimethylbenzidine was obtained in 75.0 g (0.14 mol) with a yield of 69.0%.

Table 1 shows the results of Examples 1 and 2 and Comparative Examples 1 and 3. The HFA agent is a raw material for introducing an HFIP group into the aromatic ring of diamine, and refers to HFA or HFA trihydrate (hereinafter, the same applies to Tables 2 to 3).

As shown in Table 1, in Example 1 using HFIP as the reaction solvent, the target product was obtained with a high selectivity (97.6%) and a yield (96.8%).

In Example 2, a high selectivity (97.7%) of the target product equivalent to that in Example 1 was obtained, and HFIP could be reused as a reaction solvent.

Comparative Example 1 in which the solvent was changed to HFIP and ethanol having nucleophilicity was used had a higher reaction temperature (110 ° C.), a longer reaction time (24 hours), and paratoluene acid as a catalyst as compared with Example 1. Despite the addition of monohydrate, the selectivity of the target product was low (10.6%).

In Comparative Example 2 in which acetonitrile was used as a polar solvent in which the solvent was changed to HFIP, the HFA and the amino group of the raw material metatridin or the amino group of the target HFIP group-containing diamine reacted with each other as compared with Example 1. As a result, the amount of imines produced as by-products increased, and the desired product was hardly obtained (0.4%).

Comparative Example 3 in which HFA trihydrate was used as a raw material and reacted without a solvent had a higher reaction temperature (135 ° C.), a longer reaction time (22 hours), and paratoluene sulfonic acid 1 as a catalyst as compared with Example 1. Despite the addition of hydrate, the yield of the desired product was low (69.0%).

1-2. Synthesis Example 3 of HFIP group-containing diamine having a diphenylmethane skeleton
<Synthesis of 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-methylenedianiline>
In a 1 L stainless steel pressure reactor equipped with a pressure gauge, a thermometer and a stirrer, 75.0 g (0.38 mol) of 4,4-methylenedianiline as a raw material and 750 g of HFIP as a reaction solvent are placed. After replacing the inside of the reactor with nitrogen, heat it with an oil bath, and when the internal temperature reaches 80 ° C, add 145 g (0.87 mol, 2.3 eq) of HFA and react at 80 ° C for 24 hours. Was done.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by high performance liquid chromatography (HPLC). The target product, 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-methylenedianiline, is 89.9%, HFIP group. 3-Bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-methylenedianiline in which one was introduced, 5.5% by-product imines Was 4.6%.

After completion of the reaction, the gas was cooled to room temperature (20 ° C.), the reactor was opened, and the purged gas was recovered in a glass trap in a dry ice acetone bath. Next, 600 g of toluene was placed in the reactor, HFIP, which was a reaction solvent, was distilled off at normal pressure while heating with an oil bath, 150 g of toluene was placed in the reactor, and heating was continued, and the internal temperature reached 110 ° C. At that point, it was held for 2 hours. Next, the reactor was cooled to 10 ° C., crystals of the reactants were precipitated to form a slurry, and the mixture was filtered off by a centrifuge. The obtained powder was dried under reduced pressure at 60 ° C. and 6 kPa for 2 hours to obtain the desired 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4. , 4'-Methylenedianiline white powder was obtained in 153 g (0.27 mol), yield 70.8%. The NMR measurement data of the target product is shown below.

^{1 1} H-NMR (reference substance: TMS, solvent: CD ₃ CN) δ (ppm): 7.88 (br, 1H), 7.27 (s, 2H), 7.17 (dd, 2H, J = 6) .1,2.1Hz), 6.98 (d, 2H, J = 8.1Hz), 3.88 (s, 2H). ¹⁹ F-NMR (reference substance: CCl ₃ F, solvent: CD ₃ CN δ (ppm): -75.7 (s, 12F))

1-3. Synthesis Example 4 of HFIP group-containing diamine having a diphenyl ether skeleton
<Synthesis of 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline using HFIP as a solvent>

A 1 L stainless steel pressure reactor equipped with a pressure gauge, a thermometer and a stirrer, 80.0 g (0.40 mol) of 4,4'-oxydianiline as a raw material, and 3.0 g of trifluoromethanesulfonic acid as a catalyst. (0.02 mol), 400 g of HFIP, which is a reaction solvent, was added, the inside of the reactor was replaced with nitrogen, and then heated by an oil bath. When the internal temperature reached 80 ° C., HFA, 146 g (0.88 mol). 2.2 equivalents) was added, and the reaction was carried out at 80 ° C. for 24 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled, and the composition ratio (selectivity) of the reaction product was measured by high performance liquid chromatography (HPLC). Represented by, the target 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline is 88.7%, hexa. 3.2% of 3- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline introduced with one fluoroisopropanol group was by-produced. Immins accounted for 6.2%, and others accounted for 4.9%.

Comparative Example 4
<Synthesis of 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline using xylene as a solvent>

A stainless steel pressure reactor with an internal volume of 300 mL equipped with a pressure gauge, a thermometer and a stirrer, 15.0 g (0.075 mol) of 4,4'-oxydianiline as a raw material, and paratoluenesulfonic acid 1 as a catalyst. 0.71 g (0.0038 mol) of hydrate and 45 ml of xylene as a reaction solvent were added, the inside of the reactor was replaced with nitrogen, and then heated with an oil bath. When the internal temperature reached 120 ° C., HFA, 37. 2 g (0.22 mol, 3.0 equivalents) was added and the reaction was carried out at 120 ° C. for 23 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled, and the composition ratio (selectivity) of the reactants was measured by gas chromatography. The target 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline was 39.8%, 3- (1- (1-). Hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline 5.4%, by-product imines 53.0%, others 1.8% Met.

Table 2 shows the results of Example 4 and Comparative Example 4.

As shown in Table 2, Comparative Example 4 in which xylene was used in which the solvent was changed to HFIP was different from Example 4 in that the reaction temperature was higher (120 ° C.) and the reaction time was longer (23 hours). The selection rate of things was low (39.8%).

2. 2. Synthesis Example 5 of HFIP group-containing diamine, which is an aromatic monocyclic compound
<Synthesis of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine using HFIP as a solvent>
In a 1 L stainless steel pressure resistant reactor equipped with a pressure gauge, a thermometer and a stirrer, 30.0 g (0.28 mol) of paraphenylenediamine as a raw material and 300 g of HFIP as a reaction solvent were placed in the reactor. After replacement with nitrogen, the mixture was heated with an oil bath, and when the internal temperature reached 80 ° C., 55.8 g (0.34 mol, 1.2 equivalent) of HFA was added, and the reaction was carried out at 80 ° C. for 24 hours. ..

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. 1- (2-Hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine was 73.6%, paraphenylenediamine was 17.2%, and by-produced imines were 9.2%. ..

Example 6
<Synthesis of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine using HFIP as a solvent> Addition of paratoluenesulfonic acid monohydrate as a catalyst Pressure gauge, thermometer and stirrer In a 1 L stainless steel pressure resistant reactor equipped with, 75.0 g (0.69 mol) of paraphenylenediamine as a raw material, 5.25 g (0.028 mol) of paratoluenesulfonic acid monohydrate as a catalyst, 750 g of HFIP, which is a reaction solvent, was added, the inside of the reactor was replaced with nitrogen, and then heated with an oil bath. When the internal temperature reached 80 ° C., 137 g (0.83 mol, 1.2 equivalent) of HFA was added. In addition, the reaction was carried out at 80 ° C. for 24 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. 1- (2-Hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine was 92.0%, paraphenylenediamine was 0.3%, and by-product imines were 7.7%. ..

After cooling the reactor to room temperature (20 ° C.) and terminating the reaction, the reactor was opened and the purged gas was recovered in a glass trap in a dry ice acetone bath. Next, 500 g of toluene was placed in the reactor, and HFIP, which was a reaction solvent, was distilled off at normal pressure while heating with an oil bath. When it reached, it was held for 2 hours. Next, the reactor was cooled to 10 ° C., crystals of the reactants were precipitated to form a slurry, and the mixture was filtered off by a centrifuge. The obtained powder was dried under reduced pressure at 60 ° C. and 6 kPa for 2 hours to obtain 153 g (0.58) of the desired purple powder of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine. Mol), yield 84.1%. The NMR measurement data of the target product is shown below.

^{1 1} H-NMR (reference substance: TMS, solvent: (CD ₃ ) ₂ CO) δ (ppm): 6.98 (d, 1H, J = 8.5Hz), 6.88 (m, 1H), 6. 71 (dd, 1H, J = 2.6,8.5Hz), 4.80 (br, 2H), 2.83 (br, 2H). ¹⁹ F-NMR (reference substance: CCl ₃ F, solvent: (CD ₃ ) ₂ CO) δ (ppm): -75.0 (s, 6F).

８０℃で２４時間反応させた後、反応液をサンプリングして、反応物の組成（選択率）をガスクロマトグラフィーにより測定したところ、それぞれ面積％で表して、目的とする１－（２－ヒドロキシヘキサフルオロ－２－プロピル）－２，５－フェニレンジアミンが９３．９％、パラフェニレンジアミンが２．５％、副生したイミン類が３．６％であり、実施例４の結果とほぼ同等であった。 Example 7
<Synthesis of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine using HFIP as a catalyst> Addition of trifluoromethanesulfonic acid as a catalyst Paratoluenesulfonic acid monohydrate as a catalyst The same reaction as in Example 4 was carried out in the same procedure except that trifluoromethanesulfonic acid was used instead.

After reacting at 80 ° C. for 24 hours, the reaction solution was sampled, and the composition (selectivity) of the reaction product was measured by gas chromatography. Hexafluoro-2-propyl) -2,5-phenylenediamine was 93.9%, paraphenylenediamine was 2.5%, and by-produced imines were 3.6%, which are almost the same as the results of Example 4. Met.

Comparative Example 5
<Synthesis of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine using toluene as a solvent>
In a 1 L stainless steel pressure reactor equipped with a pressure gauge, a thermometer and a stirrer, 30.0 g (0.28 mol) of paraphenylenediamine as a raw material and 2.1 g of paratoluenesulfonic acid monohydrate as a catalyst (. 0.011 mol), 300 g of toluene as a reaction solvent was added, the inside of the reactor was replaced with nitrogen, and then heated with an oil bath. When the internal temperature reached 110 ° C., HFA, 55.8 g (0.34 mol, 1.2 equivalents) was added, and the reaction was carried out at 110 ° C. for 24 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. The 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine was 19.3%, the paraphenylenediamine was 78.1%, and the others were 2.6%.

Table 3 shows the results of Examples 5 to 7 and Comparative Example 5.

As shown in Table 3, Example 6 using paratoluenesulfonic acid monohydrate as a catalyst improved the selectivity of the target product as compared with Example 5 without a catalyst (92.0%). ).

Example 7 using trifluoromethanesulfonic acid as a catalyst had the same selectivity of the target product as Example 6 using paratoluenesulfonic acid monohydrate as a catalyst (93.9%).

In Comparative Example 5 in which toluene was used as the solvent, the selectivity of the target product was lower (19.3%) than in Example 6 even though the reaction temperature was high (120 ° C.).

Example 8
[Synthesis of 1,3-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) -4,6-phenylenediamine]
A 1 L stainless steel pressure reactor equipped with a pressure gauge, a thermometer and a stirrer, 25.0 g (0.23 mol) of metaphenylenediamine as a raw material, and 3.47 g (0.023 mol) of trifluoromethanesulfonic acid as a catalyst. ) And 250 g of HFIP as a reaction solvent, the inside of the reactor was replaced with nitrogen, and then heated with an oil bath. When the internal temperature reached 80 ° C., 92.1 g of HFA (0.56 mol, 2.4 equivalents). Was added, and the reaction was carried out at 80 ° C. for 24 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. 1,3-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) -4,6-phenylenediamine 99.2%, others 0.8% Met.

Example 9
[Synthesis of 9,9-bis (4-amino-3- (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) phenyl) fluorene]
A 1 L stainless steel pressure reactor equipped with a pressure gauge, a thermometer and a stirrer, 80.0 g (0.23 mol) of 9,9-bis (4-aminophenyl) fluorene as a raw material, and trifluoromethanesulfone as a catalyst. 1.70 g (0.011 mol) of acid and 400 g of HFIP as a reaction solvent were added, the inside of the reactor was replaced with nitrogen, and then heated with an oil bath. When the internal temperature reached 80 ° C., 91.5 g (0) of HFA was added. .55 mol (2.4 equivalents) was added, and the reaction was carried out at 80 ° C. for 20 hours.

After the reactor was cooled to room temperature (20 ° C.) to complete the reaction, the reaction solution was sampled and the composition (selectivity) of the reaction product was measured by gas chromatography. 9,9-bis (4-amino-3- (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) phenyl) fluorene is 96.3%, others are 3 It was 0.7%.

As can be seen from the results of Examples 1 to 9, the method for producing an HFIP group-containing diamine of the present invention using HFIP as a solvent has less by-products of imines with respect to various aromatic diamines and corresponds to the HFIP group. The contained diamine was obtained with high selectivity and yield.

Example 10
[Synthesis of Fluorine-Containing Aromatic Polyimide by Dehydration Ring Closure Using Dehydration Reagent]
5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) synthesized in Example 1 in a 500 mL four-necked flask equipped with a nitrogen introduction tube and a stirring blade. Add 33.4 g (0.061 mol) of -2,2'-dimethylbenzidine and 27.2 g (0.061 mol) of 6FDA, and add 111 g of DMAc as an organic solvent. After stirring at 20 ° C. for 24 hours, 10.2 g (0.13 mol) of pyridine and 13.1 g (0.13 mol) of anhydrous acetic acid are added in this order, and the mixture is stirred at room temperature (20 ° C.) for 3 hours under a nitrogen atmosphere. , Imidization was performed. Then, DMAc was added to dilute the reaction solution after imidization, and the reaction solution was pressurized and filtered to synthesize a polyimide DMAc solution containing a repeating unit represented by the formula (26). When the molecular weight of the obtained polyimide solution was measured by gel permeation chromatography (hereinafter, may be abbreviated as GPC), it was found to be Mw = 120500 and Mw / Mn = 2.3. Mw is a weight average molecular weight and Mn is a number average molecular weight.

The GPC used was manufactured by Tosoh Corporation, model name: HLC-8320GPC, column: TSKgel SuperHZM-H, and THF was used as the developing solvent.

Example 11
The same operation as in Example 10 was carried out except that 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine synthesized in Example 7 for the fluorine-containing aromatic diamine was used. When the molecular weight of the polyimide solution containing the repeating unit represented by (27) was measured, it was found to be Mw = 120760 and Mw / Mn = 2.3. The model and the column were used as the GPC, and THF was used as the developing solvent.

Example 12
[Synthesis of Fluorine-Containing Aromatic Polyimide by Heat Dehydration Ring Closure]
The 5,5'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-tri) synthesized in Example 1 was placed in a 300 mL three-necked flask equipped with a nitrogen introduction tube, a toluene tube and a stirring blade. Add 43.5 g (0.08 mol) of fluoroethyl) -2,2'-dimethylbenzidine and 35.5 g (0.08 mol) of 6FDA, and add N-methyl-2-pyrrolidone (NMP) as an organic solvent. ) Was added 143 g and 50 g of toluene, and the mixture was heated in an oil bath under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 180 ° C. for 7 hours.

After cooling the reactor to room temperature (20 ° C.) and terminating the reaction, a polyimide solution containing a repeating unit represented by the formula (26) was sampled and the molecular weight was measured by GPC. As a result, Mw = 87190. , Mw / Mn = 2.1. The model and the column were used as the GPC, and THF was used as the developing solvent.

Example 13
The same operation as in Example 12 was carried out except that 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine synthesized in Example 7 for the fluorine-containing aromatic diamine was used. When the molecular weight of the obtained polyimide solution was measured, it was found that Mw = 91110 and Mw / Mn = 2.3. The model and the column were used as the GPC, and THF was used as the developing solvent.

Example 14
[Synthesis of Fluorine-Containing Aromatic Polyamide]
The 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-tri) synthesized in Example 3 was placed in a 500 mL four-necked flask equipped with a nitrogen introduction tube, a dropping funnel and a stirring blade. Fluoroethyl) -4,4'-methylenedianiline was added in an amount of 53.0 g (0.1 mol), and DMAc was added in an amount of 55 g. Next, a solution prepared by dissolving 20.3 g of terephthalic acid chloride in 55 g of THF was added by a dropping funnel under a nitrogen atmosphere while keeping the internal temperature at 10 ° C. or lower in a constant temperature bath. After the addition is completed, the internal temperature is raised to room temperature (25 ° C.) and aged for 1 hour, and then a polyamide solution containing a repeating unit represented by the formula (28) is sampled and the molecular weight is measured by GPC. As a result, Mw = 760000 and Mw / Mn = 2.2. The model and the column were used as the GPC, and THF was used as the developing solvent.

As can be seen from the results of Examples 10 to 14, in the method for producing a HFIP group-containing diamine of the present invention, a fluorine-containing polyimide of a high molecular weight substance capable of producing a self-supporting film by using the obtained fluorine-containing aromatic diamine. And a fluorine-containing polyamide was obtained.

Claims (14)

Aromatic diamine and
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
A step of obtaining a fluorine-containing aromatic diamine in which a -C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material.
A method for producing a fluorine-containing aromatic diamine.
The aromatic diamine is the formula (1).

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
Represented by
Among the aromatic diamines, the fluorine-containing aromatic diamine in which a —C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group is represented by the formula (2).

(In the equation, A and R ¹ have the same meaning as in the equation (1), and a and b independently represent integers of 0 to 2, and 1 ≦ a + b ≦ 4.)
Represented by,
A method for producing a fluorine-containing aromatic diamine. Equation (3)

(In the formula, A and R ¹ are synonymous with the meaning in the formula (1))
Aromatic diamine represented by
Hexafluoroacetone was reacted in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (4)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to claim 1 . Equation (5)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine represented by
Hexafluoroacetone was reacted in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (6)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to claim 1 or 2 . Equation (7)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Aromatic diamine represented by
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (8)

(In the formula, A and R ¹ have the same meaning as in the formula (1).)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to claim 1 or 2 . Aromatic diamine and
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
A step of obtaining a fluorine-containing aromatic diamine in which a -C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group in an aromatic diamine as a starting material .
A method for producing a fluorine-containing aromatic diamine.
The aromatic diamine is the formula (9).

Represented by
Among the aromatic diamines, the fluorine-containing aromatic diamine in which a —C (CF ₃ ) ₂ OH group is bonded to an aromatic ring having an amino group is represented by the formula (10).

(In the formula, c represents an integer of 1 to 4.)
Represented by ,
A method for producing a fluorine-containing aromatic diamine. With para-phenylenediamine,
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (11)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining a fluorine-containing aromatic diamine represented by
The method for producing a fluorine-containing aromatic diamine according to claim 5 . The fluorine-containing aromatic diamine represented by the formula (11)

It is a fluorine-containing aromatic diamine represented by.
The method for producing a fluorine-containing aromatic diamine according to claim 5 or 6 . With meta-phenylenediamine,
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (12)

(In the formula, c represents an integer of 1 to 4.)
Including the step of obtaining a fluorine-containing aromatic diamine compound represented by
The method for producing a fluorine-containing aromatic diamine according to claim 5 . The fluorine-containing aromatic diamine represented by the formula (12)

The method for producing a fluorinated aromatic diamine according to claim 5 or 8 , which is a fluorinated aromatic diamine represented by. The method for producing a fluorine-containing aromatic diamine according to any one of claims 1 to 9 , wherein the reaction is carried out in the presence of an acid. Equation (1)

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
Aromatic diamine represented by
Hexafluoroacetone
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (2)

(In the equation, A and R ¹ have the same meaning as in the equation (1), and a and b independently represent integers of 0 to 2, and 1 ≦ a + b ≦ 4.)
The first step of obtaining a fluorine-containing aromatic diamine represented by
The second step of reacting the fluorine-containing aromatic diamine represented by the formula (2) with the tetracarboxylic acid dianhydride to obtain a fluorine-containing aromatic polyamic acid, and
A third step of dehydrating and ring-closing the fluorinated aromatic polyamic acid to obtain a fluorinated aromatic polyimide is included.
A method for producing a fluorine-containing aromatic polyimide. Equation (9)

Aromatic diamine represented by
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (10)

(In the formula, c represents an integer of 1 to 4.)
The first step of obtaining a fluorine-containing aromatic diamine represented by
The second step of reacting the fluorinated aromatic diamine represented by the formula (10) with the tetracarboxylic acid dianhydride to obtain a fluorinated aromatic polyamic acid, and
A third step of dehydrating and ring-closing the fluorinated aromatic polyamic acid to obtain a fluorinated aromatic polyimide is included.
A method for producing a fluorine-containing aromatic polyimide. Equation (1)

(In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH ₂ , SO, SO ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ , or an alicyclic, heterocyclic, aromatic. It is a divalent group having a heterocyclic ring or an aromatic ring, and R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
Aromatic diamine represented by
Hexafluoroacetone
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (2)

(In the equation, A and R ¹ have the same meaning as in the equation (1), and a and b independently represent integers of 0 to 2, and 1 ≦ a + b ≦ 4.)
The first step of obtaining a fluorine-containing aromatic diamine represented by
A second step of reacting a fluorinated aromatic diamine represented by the formula (2) with a dicarboxylic acid or a derivative thereof, or a dicarboxylic acid dihalide to obtain a fluorinated aromatic polyamide.
A method for producing a fluorine-containing aromatic polyamide. Equation (9)

Aromatic diamine represented by
Hexafluoroacetone,
Reaction in 1,1,1,3,3,3-hexafluoro-2-propanol and
Equation (10)

(In the formula, c represents an integer of 1 to 4.)
The first step of obtaining a fluorine-containing aromatic diamine represented by
A second step of reacting a fluorinated aromatic diamine represented by the formula (10) with a dicarboxylic acid or a derivative thereof, or a dicarboxylic acid dihalide to obtain a fluorinated aromatic polyamide.
A method for producing a fluorine-containing aromatic polyamide.