CN111263761A - Novel polymer and diamine compound - Google Patents

Abstract

The present invention relates to a diamine compound represented by the following general formula (1). In formula (1) herein, R¹、R²、R³And R⁴Each independently representing H, CH₃Or CF₃Wherein R is¹、R²、R³And R⁴Of which one must represent CH₃Or CF₃，W₁Represents a single bond or phenylene group, W₂Represents phenylene, L represents a C1-10 linear or branched alkylene group, and CH of the alkylene group₂Optionally substituted by oxygen atom or the like. The present invention can provide a diamine which can be easily provided with various properties by using a highly available raw material, and further can provide a diamine obtained therefromNovel polymers.

Description

Novel polymer and diamine compound

Technical Field

The present invention relates to: a novel diamine compound (also referred to simply as "diamine" in the present invention) useful as a raw material for a polymer used for a liquid crystal alignment film, and a polymer obtained using the diamine. The present invention relates to, for example, a polyimide suitable for an electronic material and a diamine compound as a raw material monomer thereof, if described in detail further.

Background

In general, polyimide resins are widely used as protective materials and insulating materials for liquid crystal display elements and semiconductors, and as electronic materials such as color filters, because of their high mechanical strength, heat resistance, insulating properties, and solvent resistance, which are characteristics of polyimide resins. In addition, recently, the material is expected to be used as a material for optical communication such as a material for optical waveguide.

In recent years, the development in this field has been remarkable, and in response to this, high-level characteristics have been increasingly demanded also for materials to be used. That is, it is expected that the composition not only has excellent heat resistance and solvent resistance but also has various performances suitable for the intended use.

However, polyimides, particularly polyimides produced from pyromellitic anhydride (PMDA) and 4, 4' -dioxyaniline (ODA) (trade name) which are generally used as typical examples of wholly aromatic polyimide resins, are not used in the form of a solution because of their poor solubility, and are obtained by heating and dehydrating a precursor called polyamic acid.

In addition, in the polyimide having solvent solubility (hereinafter referred to as soluble polyimide), since amide-based and lactone-based organic solvents having high solubility such as N-methyl-2-pyrrolidone (NMP) and γ -butyrolactone, which have been conventionally used, have high boiling points, high-temperature firing for removing the solvent is unavoidable.

In the field of liquid crystal display elements, research and development have been recently carried out on flexible liquid crystal display elements using plastic substrates, and if high-temperature firing is carried out, the deterioration of element components becomes a problem, and therefore, low-temperature firing has become desired in recent years.

On the other hand, polyamic acids exhibiting high solvent solubility have the following problems: sufficient liquid crystal display characteristics cannot be obtained, and a volume change due to imidization is likely to occur, and polyimide which is soluble in an organic solvent having a low boiling point is desired.

As a solution to this problem, a synthesis method of tetracarboxylic dianhydride using an alicyclic dicarboxylic anhydride which is advantageous in solubility in organic solvents is considered. As an example thereof, it is known that various acid dianhydrides can be produced by using trimellitic anhydride acid chloride or nuclear hydrogenation trimellitic anhydride acid chloride as a raw material (for example, patent document 1).

On the other hand, as in the case of the acid dianhydride, a method for imparting various properties to a diamine using an inexpensive raw material has not been known so far.

Documents of the prior art

Patent document

Patent document 1: WO2006/129771 pamphlet

Disclosure of Invention

Problems to be solved by the invention

To date, several diamines having an imide ring have been reported, but the solubility is low, and therefore, it has been pointed out that the diamines do not dissolve, or do not increase in molecular weight.

An object of the present invention is to provide: by using commercially available raw materials which are inexpensive and highly available, a method for producing a diamine having high solubility and various properties which cannot be obtained unless a polymer of polyamic acid obtained from a diamine and an acid dianhydride is imidized, a diamine obtained by the method, and a novel polymer obtained by the method can be easily provided.

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, have found that: the present inventors have found that a method for producing a polymer, which uses a conventional diamine compound having a linear or branched alkylene group and a commercially available compound that is inexpensive and highly available as raw materials, can easily impart various properties that cannot be obtained without imidizing a polymer of polyamic acid obtained from a diamine and an acid dianhydride, and have completed the present invention.

The present invention is based on the above findings and the gist thereof is as follows.

<1> a diamine compound represented by the following general formula (1).

In the formula (1), the reaction mixture is,

R¹、R²、R³and R⁴Each independently representing H, CH₃Or CF₃Wherein R is¹、R²、R³And R⁴Of which one must represent CH₃Or CF₃，

W₁Represents a single bond or a phenylene group, the phenylene group is optionally substituted by a substituent selected from group 1 consisting of a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (each of the alkyl groups is independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, a linear or branched acyl group having 1 to 10 carbon atoms, a carboxyl group, an aldehyde group, a nitro group, and an amino group protected by Boc, and 2W is₁Optionally the same or different from each other,

W₂represents a phenylene group optionally substituted with a substituent selected from the above group 1, 2W₂Optionally the same or different from each other,

l represents a linear or branched alkylene group having 1 to 10 carbon atoms which is optionally substituted with a substituent selected from the group 1, and-CH in L₂-is optionally selected from-CH ═ CH-, -C ≡ C-, -CF₂-、-C(CF₃)₂-、-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-N(CH₃)-、-NHCONH-、-N(Boc)CONH-、-NHCON(Boc)-、-N(Boc)CON(Boc)-、-NHCOO-、-OCONH-、-CO-、-S-、-SO₂-、-N(Boc)-、-Si(CH₃)₂OSi(CH₃)₂-、-Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂-, a piperidine ring and a piperazine ringWherein the groups selected from group 2 are optionally adjacent to each other under the condition that the same atoms other than carbon atoms are not bonded.

<2> a polymer obtained from the diamine compound represented by the above formula (1).

ADVANTAGEOUS EFFECTS OF INVENTION

By using the liquid crystal aligning agent containing the polymer of the present invention, it is possible to provide: a liquid crystal alignment film having high voltage holding ratio and abrasion resistance and capable of rapidly relaxing accumulated charges; and a liquid crystal display element having excellent characteristics.

Detailed Description

The present invention, as described above, relates to: a diamine compound represented by the formula (1) (hereinafter, sometimes referred to as a specific diamine), and a polymer obtained from the diamine compound.

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer (hereinafter, also referred to as a specific polymer) obtained from a diamine having a structure represented by the above formula (1).

Each condition will be described in detail below.

< specific diamine >

As described above, the diamine compound of the present invention is represented by the formula (1). The substituents of formula (1) are defined herein below.

R¹、R²、R³And R⁴Each independently representing H, CH₃Or CF₃Wherein R is¹、R²、R³And R⁴Of which one must represent CH₃Or CF₃，

W₁Represents a single bond or a phenylene group, the phenylene group is optionally substituted by a substituent selected from group 1 consisting of a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (each of the alkyl groups is independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, a linear or branched acyl group having 1 to 10 carbon atoms, a carboxyl group, an aldehyde group, a nitro group, and an amino group protected by Boc, and 2W is₁Optionally the same or different from each other,

W₂represents a phenylene group optionally substituted with a substituent selected from the above group 1, 2W₂Optionally the same or different from each other,

l represents a linear or branched alkylene group having 1 to 10 carbon atoms which is optionally substituted with a substituent selected from the group 1, and-CH in L₂-is optionally selected from-CH ═ CH-, -C ≡ C-, -CF₂-、-C(CF₃)₂-、-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-N(CH₃)-、-NHCONH-、-N(Boc)CONH-、-NHCON(Boc)-、-N(Boc)CON(Boc)-、-NHCOO-、-OCONH-、-CO-、-S-、-SO₂-、-N(Boc)-、-Si(CH₃)₂OSi(CH₃)₂-、-Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂-, a piperidine ring and a piperazine ring, wherein the groups selected from group 2 are optionally adjacent to each other under the condition that the same atoms other than carbon atoms are not bonded to each other.

R¹、R²、R³And R⁴Each independently representing H, CH₃Or CF₃Wherein R is¹、R²、R³And R⁴Of which one must represent CH₃Or CF₃。

Among them, from the viewpoint of high solubility, R is preferably¹And R⁴Represents CH₃Or CF₃、R²And R³Represents a hydrogen atom, more preferably R¹And R⁴Represents a methyl group, R²And R³Represents a hydrogen atom.

As W₁Preferably a single bond or 1, 4-phenylene.

As W₂1, 4-phenylene is preferred.

The alkylene group having 1 to 10 carbon atoms of L may be a straight chain or a branched chain, and examples thereof include: - (CH)₂)_n- (wherein n is a straight-chain alkylene group represented by 1 to 10), 1-methyl methane-1, 1-diyl group, 1-ethyl methane-1, 1-diyl group, a salt thereof, a hydrate,1-propylmethane-1, 1-diyl, 1-methylethyl-1, 2-diyl, 1-ethylethane-1, 2-diyl, 1-propylethane-1, 2-diyl, 1-methylpropane-1, 3-diyl, 1-ethylpropane-1, 3-diyl, 1-propylpropane-1, 3-diyl, 2-methylpropane-1, 3-diyl, 2-ethylpropane-1, 3-diyl, 2-propylpropane-1, 3-diyl, 1-methylbutane-1, 4-diyl, 1-ethylbutane-1, 4-diyl, 1-propylbutane-1, 4-diyl, 2-methylbutane-1, 4-diyl, 2-ethylbutane-1, 4-diyl, 2-propylbutane-1, 4-diyl, 1-methylpentane-1, 5-diyl, 1-ethylpentane-1, 5-diyl, 1-propylpentane-1, 5-diyl, 2-methylpentane-1, 5-diyl, 2-ethylpentane-1, 5-diyl, 2-propylpentane-1, 5-diyl, 3-methylpentane-1, 5-diyl, 3-ethylpentane-1, 5-diyl, 3-propylpentane-1, 5-diyl, 1-methylhexane-1, 6-diyl, Branched alkylene groups such as 1-ethylhexane-1, 6-diyl, 2-methylhexane-1, 6-diyl, 2-ethylhexane-1, 6-diyl, 3-methylhexane-1, 6-diyl, 3-ethylhexane-1, 6-diyl, 1-methylheptane-1, 7-diyl, 2-methylheptane-1, 7-diyl, 3-methylheptane-1, 7-diyl, 4-methylheptane-1, 7-diyl, 1-phenylmethane-1, 1-diyl, 1-phenylethane-1, 2-diyl and 1-phenylpropane-1, 3-diyl.

These straight-chain or branched alkylene groups (-CH)₂-) is optionally selected from the group consisting of-CH- ═ CH-, -C.ident.C-, -CF₂-、-C(CF₃)₂-、-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-N(CH₃)-、-NHCONH-、-N(Boc)CONH-、-NHCON(Boc)-、-N(Boc)CON(Boc)-、-NHCOO-、-OCONH-、-CO-、-S-、-SO₂-、-N(Boc)-、-Si(CH₃)₂OSi(CH₃)₂-、-Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂-, a piperidine ring, and a piperazine ring, or a group of group 2.

Wherein, at this time, the groups selected from group 2 are optionally adjacent to each other under the condition that the same atom other than carbon atom is not bonded. In other words, in the case where a plurality of groups selected from group 2 capable of substituting an alkylene group are present, in the case where the bonding portions between the groups selected from group 2 are bonded to each other with the same atom other than carbon atoms, the groups selected from group 2 cannot be adjacent to each other. The bonding portions between the groups selected from group 2 can bond the groups selected from group 2 to each other if the carbon atoms are bonded to each other or are bonded with different atoms from each other. Preferably, the bonding portions between the groups selected from group 2 are, if carbon atoms are each other, capable of bonding the groups selected from group 2 to each other.

According to other modes of the invention, the groups selected from group 2 are not adjacent to each other.

As W¹-L-W²Preferred structures of the present invention include, but are not limited to, the following structures.

< Process for producing specific diamine >

The method for obtaining the diamine will be described below.

The method for synthesizing the specific diamine of the present invention is not particularly limited, and examples thereof include the following methods: a compound represented by the following formula (C) is obtained by reacting a bismaleimide compound represented by the following formula (A) with a compound represented by the following formula (B), and then the compound is imidized to obtain a compound represented by the following formula (D), and then the compound is converted into a compound represented by the formula (1).

In the formula, R¹、R²、R³、R⁴、W₁、W₂And L represents the aforementioned meaning, Q represents NO₂Or a protected amino group (NHPro).

Examples of the protecting group (Pro) for an amino group include, but are not limited to, acetyl, trifluoroacetyl, pivaloyl, t-butoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, 2,2, 2-trichloroethoxycarbonyl, benzyloxycarbonyl, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, t-butyldimethylsilyl, t-butyldiethylsilyl, 9-fluorenylmethyloxycarbonyl, phthaloyl, allyloxycarbonyl, p-toluenesulfonyl, and o-nitrobenzenesulfonyl.

The amount of the compound represented by the formula (B) to be used is preferably 2 to 4 moles, and more preferably 2 to 2.5 moles, relative to 1 mole of the compound represented by the formula (a). By making the compound represented by the formula (B) in an excess amount, the reaction proceeds smoothly and by-products are suppressed.

The reaction is preferably carried out in a solvent.

The solvent may be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents such as DMF, DMSO, DMAc and NMP; et (Et)₂O、i-Pr₂O, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), dioxane, and other ethers; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetrahydronaphthalene; halogen hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; nitriles such as acetonitrile, propionitrile, and butyronitrile; and the like.

These solvents may be appropriately selected in consideration of the easiness of reaction, and may be used alone in 1 kind or in combination of 2 or more kinds. If necessary, the solvent may be dried with a dehydrating agent or a drying agent to prepare a nonaqueous solvent.

The amount of the solvent used (reaction concentration) is not particularly limited, and is 0.1 to 100 times by mass relative to the bismaleimide compound. Preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited, but is in the range of-100 ℃ to the boiling point of the solvent used, preferably-50 to 150 ℃. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

The reaction may be carried out in the presence of an inorganic base or an organic base, if necessary.

As the base used in the reaction, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, and the like; bases such as sodium tert-butoxide, potassium tert-butoxide, sodium hydride and potassium hydride; and amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, and collidine. Among them, triethylamine, pyridine, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride and the like are preferable.

The amount of the base used is not particularly limited, and is 0.1 to 100 times by mass based on the bismaleimide compound. Preferably 0 to 30 times by mass, and more preferably 0 to 10 times by mass.

The compound represented by the formula (D) can be obtained by imidizing the compound represented by the formula (C).

In the case of performing imidization, chemical imidization in which a catalyst is added to a solution of a compound represented by formula (C) obtained by a reaction between an amine component and a bismaleimide compound is simple. Chemical imidization is preferred because the imidization reaction proceeds at a relatively low temperature and decomposition of Pro groups is less likely to occur during the imidization.

Chemical imidization can be carried out by stirring a compound to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. The organic solvent used in the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ -butyrolactone, etc. from the viewpoint of solubility, and 1 kind or 2 or more kinds mixed may be used.

The concentration of the compound is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint of preventing the compound from being easily precipitated.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. The acid anhydride may be acetic anhydride, trimellitic anhydride, pyromellitic anhydride, or the like, and among these, acetic anhydride is preferred because purification after completion of the reaction is easy.

The temperature for the imidization reaction is-20 to 140 ℃, preferably 0 to 100 ℃, and the reaction time may be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times by mol, preferably 2 to 20 times by mol, and the amount of the acid anhydride is 1 to 50 times by mol, preferably 3 to 30 times by mol, based on the amic acid group.

In the following description, Q is NO₂In the case of (3), the condition for producing the specific diamine represented by the formula (1) by reducing the compound represented by the formula (D).

The catalyst used in the reduction reaction is preferably an activated carbon-supported metal which is commercially available, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. Further, a metal catalyst which is not necessarily supported on activated carbon, such as palladium hydroxide, platinum oxide, and raney nickel, may be used. Generally, palladium-activated carbon, which is widely used, is preferable because good results can be obtained.

These reactions are carried out under a hydrogen atmosphere, under normal pressure, or under pressurized conditions. In addition, the nitro group may be reduced by using a metal such as iron, tin, or zinc, or a metal salt thereof together with a proton source. The metal and the metal salt may be used alone or in combination of 2 or more.

As the proton source, an acid such as hydrochloric acid, an ammonium salt such as ammonium chloride, or a protic solvent such as methanol or ethanol can be used.

In order to more efficiently perform the reduction reaction, the reaction may be performed in the presence of activated carbon. In this case, the amount of the activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass, based on the dinitro compound (D). In addition, in order to more efficiently perform the reduction reaction, the reaction may be performed under pressure. In the above case, the reduction of the benzene nucleus is carried out in a pressurized range of up to 20 atmospheres. The reaction is preferably carried out in a range of up to 10 atmospheres.

The solvent may be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents such as DMF, DMSO, DMAc and NMP; et (Et)₂O、i-Pr₂Ethers such as O, TBME, CPME, THF and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetrahydronaphthalene; halogen hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; nitriles such as acetonitrile, propionitrile, and butyronitrile; alcohols such as methanol and ethanol; and the like. These solvents may be appropriately selected in consideration of the easiness of reaction, and may be used alone in 1 kind or in combination of 2 or more kinds. If necessary, the solvent may be dried with a suitable dehydrating agent or drying agent to prepare a nonaqueous solvent.

The amount of the solvent (reaction concentration) is not particularly limited, and is 0.1 to 100 times by mass relative to the dinitro compound. Preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited, but is in the range of-100 ℃ to the boiling point of the solvent used, preferably-50 to 150 ℃. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

The conditions for producing the specific diamine represented by the formula (1) by deprotecting the compound represented by the formula (D) when Q is a protected amine (NHPro) will be described below.

The deprotection method of the protecting group is not particularly limited, and the target compound can be obtained by hydrolysis in the presence of an acid or a base and then neutralization. Examples of the acid to be used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid, and examples of the base to be used include inorganic bases such as sodium hydroxide, sodium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate, and organic amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, and collidine. In addition, deprotection can also be performed using a lewis acid compound such as aluminum chloride or trifluoroborane-diethyl ether complex. In addition, debenzylation reaction under hydrogen atmosphere may also be performed. Further, acids, inorganic bases, ammonium salts, and the like containing fluorine such as hydrofluoric acid, cesium fluoride, potassium fluoride, tetrabutylammonium fluoride, and the like can also be used.

The solvent may be used as long as it does not inhibit hydrolysis, and aprotic polar organic solvents such as DMF, DMSO, DMAc and NMP, Et and the like may be used₂O、i-Pr₂Ethers such as O, TBME, CPME, THF, dioxane, etc., aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, etc., aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc., halogen hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc., methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (lower fatty acid esters such as acetonitrile, propionitrile, butyronitrile, etc., alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc., or water. These solvents can be suitably selected in consideration of the easiness of causing the reaction, and in the above case, the above solvents can be used alone in 1 kind or in a mixture of 2 or more kinds. In addition, considering the use of Lewis acid, etc., it is also possible to use a nonaqueous solvent using an appropriate dehydrating agent or drying agent.

The reaction temperature may be arbitrarily selected from the range of-100 ℃ to the boiling point of the solvent used, and is preferably in the range of-50 to 150 ℃. The reaction time can be arbitrarily selected within the range of 0.1-1000 hours.

[ production method of formula (B) ]

Among the compounds represented by the formula (B), the compound (B1) wherein Q is NHPro can be obtained by reacting a diamine represented by the following formula (B1-1) with an acid chloride or acid anhydride of an amine protecting group (Pro). At this time, as a diamine(B1-1), a symmetric diamine is preferable from the viewpoint of suppressing complication of the reaction. In the formula, W₁、W₂L, Pro represents the aforementioned meaning.

Examples of (Pro) -Cl include but are not limited to methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, tert-butyl chloroformate, benzyl chloroformate, 9-fluorene chloroformate, acetyl chloride, trifluoroacetyl chloride, pivaloyl chloride, tert-butoxycarbonyl chloride, ethoxycarbonyl chloride, isopropoxy carbonyl chloride, 2,2, 2-trichloroethoxycarbonyl chloride, benzyloxycarbonyl chloride, trimethylchlorosilane, triethylchlorosilane, dimethylphenylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiethylchlorosilane, 9-fluorenylmethyloxycarbonyl chloride, phthaloyl chloride, allyloxycarbonyl chloride, p-toluenesulfonyl chloride, and o-nitrobenzenesulfonyl chloride.

As (Pro)₂Examples of O include dimethyl dicarbonate, diethyl dicarbonate, di-t-butyl dicarbonate, and dibenzyl dicarbonate, but are not limited thereto.

The reaction to obtain the compound represented by the above formula (B1) is preferably carried out in the presence of a base. As the base, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, and trimethylpyridine; sodium hydride, potassium hydride, sodium tert-butoxide, potassium tert-butoxide, and the like. When a base is used, amines are preferably used in view of the operability of the post-treatment of the reaction.

The reaction solvent may be any solvent which is stable under the reaction conditions, inactive, and does not inhibit the desired reaction. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, and N-methylpyrrolidone; ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetrahydronaphthalene; halogen hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; nitriles such as acetonitrile, propionitrile, and butyronitrile.

These solvents may be appropriately selected in consideration of the easiness of reaction, and may be used alone in 1 kind or in combination of 2 or more kinds. The solvent may be a water-free solvent such as a dehydrating agent or a drying agent.

The reaction temperature is preferably selected from a temperature range of from-100 ℃ or higher to the boiling point of the reaction solvent to be used, more preferably from-50 to 150 ℃, and particularly preferably from 0 to 60 ℃. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 50 hours.

The compound represented by formula 2 obtained by the reaction formula (1) may be purified by distillation, recrystallization, column chromatography on silica gel or the like, or may be used in the next step without purification.

In the compound represented by the formula (B), Q is NO₂The compound (B2) can be obtained by deprotecting a compound represented by the following formula (B2-1). As the deprotection conditions, the aforementioned methods can be used. In the formula, W₁、W₂L, Pro represents the aforementioned meaning.

The compound represented by the formula (B2-1) can be obtained by reacting a halogenated and sulfonylated { methanesulfonyl (OMs), ethanesulfonyl (OEs), p-toluenesulfonyl (OTs), trifluoromethanesulfonyl (OTf), etc. } compound represented by the following formula (B2-3) with a nitrated phenol represented by the following formula (B2-4). In the formula, W₁、W₂Denotes the aforementioned meaning, L¹Represents the removal of 1 CH from the aforementioned L₂(strictly speaking, CH substituted by oxygen atom)₂) WhileThe resulting alkylene group.

The compound represented by the formula (B2-3) and the nitrated phenol represented by the formula (B2-4) used as starting materials in the reaction in this step can be obtained as commercially available products or can be produced by known methods.

The reaction form may be either a rotary type (batch type) or a flow-through type.

The reaction is preferably carried out in the presence of a base. Examples of the base include 1 to 4 equivalents of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an alkali metal bicarbonate such as sodium bicarbonate or potassium bicarbonate, and an organic base such as potassium phosphate or 1, 8-diazabicyclo [5,4,0] -7-undecene, relative to the compound represented by formula (B2-3).

Among them, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferable. The use of fine powder of potassium carbonate is particularly preferable because the reactivity is improved. As commercially available fine potassium carbonate powder, FG-F20 (manufactured by Asahi glass Co., Ltd.) (registered trademark) and the like are available.

The reaction solvent is preferably Dimethylformamide (DMF), dimethylacetamide (DMAc), 1, 3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), or N-methylpyrrolidone, and particularly preferably N-methylpyrrolidone.

The reaction temperature is, for example, -10 to 100 ℃, preferably 0 to 80 ℃.

In the case of batch treatment, the reaction time is 0.5 to 20 hours, preferably 1 to 15 hours.

The reaction is preferably carried out in a solvent. The preferred solvent and reaction conditions are the same as those for producing the compound (1).

The target product in each stage obtained by each reaction may be purified by distillation, recrystallization, or chromatography on silica gel or the like, or the reaction solution may be supplied to the next stage without purification.

< Polymer >

The polymer of the present invention is a polymer obtained by using the diamine. Specific examples thereof include polyamic acids, polyamic acid esters, polyimides, polyureas, and polyamides.

< diisocyanate component >

Examples of the diisocyanate component that provides the polyamide by the reaction with the diamine represented by the above general formula (1) include aromatic diisocyanates, aliphatic diisocyanates, and the like. Preferred diisocyanate components are aromatic diisocyanates and aliphatic diisocyanates.

Here, the aromatic diisocyanate means that the group Y of the diisocyanate structure (O ═ C ═ N-Y-N ═ C ═ O) contains a structure containing an aromatic ring. The term "aliphatic diisocyanate" means that the group Y of the isocyanate structure is composed of a cyclic or acyclic aliphatic structure.

Specific examples of the aromatic diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (e.g., toluene 2, 4-diisocyanate), 1, 4-diisocyanato-2-methoxybenzene, 2, 5-diisocyanatodiphenylmethane, 2 '-bis (4-diisocyanatophenyl) propane, 4' -diisocyanatodiphenylmethane, 4 '-diisocyanatodiphenyl ether, 4' -diisocyanatodiphenylsulfone, 3 '-diisocyanatodiphenylsulfone, and 2, 2' -diisocyanatodiphenylmethanone. Preferred examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene 2, 4-diisocyanate.

Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate. The aliphatic diisocyanate is preferably isophorone diisocyanate. Among these, isophorone diisocyanate and 2, 4-tolylene diisocyanate are preferred from the viewpoint of polymerization reactivity, and isophorone diisocyanate is more preferred from the viewpoint of availability and polymerization reactivity.

< tetracarboxylic dianhydride >

The tetracarboxylic dianhydride which is a component providing a polyimide (precursor) by a reaction with the diamine represented by the above general formula (1) is represented by the following formula (X).

X₁The organic group having a valence of 4 derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. In addition, X in the polyimide precursor₁The amount of the polymer to be used may be appropriately selected depending on the degree of desired properties such as solubility in a solvent, coatability when used as a liquid crystal aligning agent, alignment of liquid crystal when forming a liquid crystal alignment film, voltage holding ratio, charge accumulation, and the like, and may be 1 kind or 2 or more kinds mixed in the same polymer.

If X is to be shown₁Specific examples of (4) include the structures of formulae (X-1) to (X-46) described in items 13 to 14 of International patent publication No. 2015/119168.

Hereinafter, preferred X is shown₁The present invention is not limited to the above.

< dicarboxylic acid >

Specific examples of the monomer compound for constituting the dicarboxylic acid component which provides the polyamide by the reaction with the diamine represented by the above general formula (1) include: terephthalic acid, isophthalic acid, 2-methyl-isophthalic acid, 4-methyl-isophthalic acid, 5-allyloxy-isophthalic acid, 5-allyloxycarbonyl-isophthalic acid, 5-propargyloxy-isophthalic acid, 5-acetoxy-isophthalic acid, 5-benzoylamide-isophthalic acid, tetrafluoroisophthalic acid, methyl terephthalic acid, tetrafluoroterephthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 6-anthracenedicarboxylic acid, 1, 6-anthracenedicarboxylic acid, 4 ' -dicarboxybiphenyl, 3,4 ' -dicarboxybiphenyl, 2,3 ' -dicarboxybiphenyl, 2,4 ' -dicarboxybiphenyl, 4 ' -dicarboxydiphenyl ether, 3,4 ' -dicarboxydiphenyl ether, 2,3 ' -dicarboxydiphenyl ether, 2,4 ' -dicarboxydiphenyl ether, 3 ' -dimethyl-4, 4 ' -dicarboxybiphenyl, 4 ' -dimethyl-3, 3 ' -dicarboxybiphenyl, 2 ' -dimethyl-4, 4 ' -dicarboxybiphenyl, 3 ' -dimethoxy-4, 4 ' -dicarboxybiphenyl, 4 ' -dimethoxy-3, 3 ' -dicarboxybiphenyl, 2 ' -dimethoxy-4, 4 ' -dicarboxybiphenyl, 4 ' -dicarboxybenzophenone, 3 ' -dicarboxybenzophenone, 2,4 ' -dicarboxybenzophenone, 3 ' -dicarboxybenzopheno, 4,4 '-dicarboxydiphenylmethane, 3' -dicarboxydiphenylmethane, 4 '-dicarboxydiphenylamide, 3, 4-dicarboxydiphenylamide, 4' -dicarboxydiphenylsulfone, 3 '-dicarboxydiphenylsulfone, 2' -dicarboxydiphenylpropane, 1, 4-bis (4-carboxyphenoxy) benzene, 1, 3-bis (4-carboxyphenoxy) benzene, N- [3{ (4-carboxyphenyl) carbonylamino } phenyl ] (4-carboxyphenyl) carboxamide, N- [4{ (4-carboxyphenyl) carbonylamino } phenyl ] (4-carboxyphenyl) carboxamide, N-bis (4-carboxyphenyl) carboxamide, N-hydroxyben, 4,4 ' - (4-carboxyphenoxyphenyl) methane, 4 ' -bis (4-carboxyphenoxy) diphenylsulfone, 2 ' -bis [4- (4-carboxyphenoxy) phenyl ] propane, 2-bis (4-carboxyphenyl) hexafluoropropane, 2 ' -bis [4- (4-carboxyphenoxy) phenyl ] hexafluoropropane, 1, 5-bis (4-carboxyphenyl) pentane, 1, 4-bis (4-carboxyphenyl) butane, 1, 3-bis (4-carboxyphenyl) propane, 4 ' -bis (carboxyphenyl) pentane-1, 5-dioate, 4 ' -bis (carboxyphenyl) hexane-1, 6-dioate, 4 ' -bis (carboxyphenyl) heptane-1, 7-dicarboxylic acid esters and other aromatic or aromatic-containing dicarboxylic acids and acid halides and alkyl esters thereof.

Further, alicyclic dicarboxylic acids such as 1, 3-dicarboxylcyclohexane, 1, 4-dicarboxylcyclohexane, 1, 2-dicarboxylcyclobutane, 1, 3-dicarboxylcyclobutane, bis (4-carboxycyclohexyl) methane, bis (4-carboxy-3-methylcyclohexyl) methane, bis (4-carboxycyclohexyl) ether and bis (4-carboxy-3-methylcyclohexyl) ether, and acid halides and alkyl esters thereof may be used, and a mixture of 2 or more kinds of them may also be used.

When the polymer of the present invention is obtained by polymerization reaction with a diamine component containing the diamine compound represented by the above formula (1), a known synthesis method can be used. In general, the method is a method of reacting at least one member selected from the group consisting of a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component with a diamine component in an organic solvent. It is advantageous in that the reaction of at least one member selected from the group consisting of the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component with the diamine component proceeds relatively easily in an organic solvent and no by-product is produced.

The organic solvent used for the reaction of the diamine component with at least one selected from the group consisting of the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component is not particularly limited as long as the resulting polymer is dissolved. Specific examples thereof will be given below.

Examples of the organic solvent that can be used here include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, γ -butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, and the like, Dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, propylene glycol monoethyl, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like. These may be used alone or in combination.

In addition, the organic solvent is preferably used as dehydrated and dried as much as possible because moisture in the organic solvent causes inhibition of the polymerization reaction.

When at least one member selected from the group consisting of a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component is reacted with a diamine component in an organic solvent, the following method may be mentioned: a method of stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and adding at least one selected from the group consisting of a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component as it is or dispersing or dissolving the diamine component in an organic solvent; conversely, a method of adding a diamine component to a solution in which at least one selected from the group consisting of a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component is dispersed or dissolved in an organic solvent; a method of alternately adding at least one member selected from the group consisting of a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component and a diamine component; and the like, and any of these methods can be used. In addition, when at least one or a diamine component selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component contains a plurality of compounds, the reaction may be performed in a state of being mixed in advance, or the reaction may be performed in sequence, and further, the low molecular weight materials after the respective reactions may be mixed and reacted to prepare a high molecular weight material.

The polymerization temperature at this time may be selected from any temperature of-20 ℃ to 150 ℃, preferably from the range of-5 ℃ to 100 ℃. The reaction may be carried out at any concentration, and if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes excessively high, and uniform stirring becomes difficult, and therefore, the total concentration in the reaction solution of at least one selected from the diisocyanate component, the dicarboxylic acid component, and the tetracarboxylic acid component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be initially carried out at a high concentration, and then the organic solvent may be added.

In the polymerization reaction of the polymer of the present invention, the ratio of the total number of moles of at least one selected from the group consisting of the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similarly to the ordinary polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polymer produced.

When the polymer produced is recovered from the reaction solution of the polymer of the present invention, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by being put into the poor solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or dried by heating. Further, the polymer after the precipitation recovery is redissolved in an organic solvent and then reprecipitated and recovered, and when the operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons and the like, and if 3 or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

In the polymer of the present invention, the polyurea is, for example, a polymer having a repeating unit represented by the following formula [1 ].

(formula [1]]In (A)₁Is an organic radical having a valence of 2, A₂Is a 2-valent group represented by the following formula (A2),

in the formula (A2), R¹、R²、R³、R⁴、W₁、W₂And L represents the aforementioned meaning, C₁And C₂Are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and are optionally the same or different. )

The above formula [1]In (A) can be₁And A₂1 type of polymer having the same repeating unit, or A₁、A₂Is a polymer with a plurality of repeating units with different structures.

The above formula [1]In (A)₁Are groups derived from the diisocyanate component as the starting material. In addition, A₂Is a group derived from a diamine component as a raw material.

According to a preferred mode of the present invention, A is₁Preference is given to groups derived from the preferred diisocyanate components listed above.

The polyimide precursor is, for example, a polymer having a repeating unit represented by the following formula [2 ].

Formula [2]]In (A)₃Each independently being a 4-valent organic radical, A₂Is a 2-valent group represented by the above formula (A2). R₁₁Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, C₁～C₂Each independently represents a hydrogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.

As R₁₁Specific examples of the alkyl group in (b) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. From the viewpoint of easiness of imidation by heating, R₁₁Preferably a hydrogen atom or a methyl group.

The polyamide is, for example, a polymer having a repeating unit represented by the following formula [3 ].

Formula [3]In (A)₄Each independently being a 2-valent organic radical derived from a dicarboxylic acid₂、C₁And C₂As described above.

In the production of the polymer of the present invention, 2 or 3 of the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component may be reacted simultaneously or sequentially, and for example, when the diisocyanate component and the tetracarboxylic acid component are reacted, a polyurea polyamic acid which is a polymer having the repeating unit represented by the above formula [1] and the repeating unit represented by the above formula [2] can be obtained.

< method for producing Polyamic acid >

The polyamic acid used as the polyimide precursor in the present invention can be synthesized by the following method.

Specifically, the tetracarboxylic dianhydride and the diamine are reacted in the presence of an organic solvent at-20 to 150 ℃, preferably 0 to 70 ℃, for 30 minutes to 24 hours, preferably 1 to 12 hours, to synthesize the polyimide.

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ -butyrolactone, or the like, from the viewpoint of solubility of the monomer and the polymer, and these may be used in 1 kind or in a mixture of 2 or more kinds.

The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint of preventing precipitation of the polymer and facilitating the production of a high molecular weight product.

The polyamic acid obtained as described above can be recovered by pouring the reaction solution into a poor solvent while sufficiently stirring the reaction solution, thereby precipitating a polymer. Further, the precipitation is performed a plurality of times, and after washing with a poor solvent, drying at room temperature or drying by heating is performed, whereby a powder of the purified polyamic acid can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, and toluene, and water, methanol, ethanol, and 2-propanol are preferable.

< method for producing polyimide >

The polyimide used in the present invention can be produced by imidizing the polyamic acid.

In the case of producing a polyimide from a polyamic acid, chemical imidization by adding a catalyst to a solution of the polyamic acid obtained by the reaction of a diamine component and a tetracarboxylic dianhydride is simple. Chemical imidization is preferred because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not easily reduced during the imidization.

Chemical imidization can be carried out as follows: the imidization is carried out by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, a solvent used in the polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. The acid anhydride may be acetic anhydride, trimellitic anhydride, pyromellitic anhydride, or the like, and among these, acetic anhydride is preferred because purification after completion of the reaction is easy.

The temperature for the imidization reaction is-20 to 140 ℃, preferably 0 to 100 ℃, and the reaction time may be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times by mol, preferably 2 to 20 times by mol, and the amount of the acid anhydride is 1 to 50 times by mol, preferably 3 to 30 times by mol, based on the amount of the polyamic acid group. The imidization ratio of the obtained polymer is controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.

Since the catalyst and the like to be added remain in the solution after the imidization of the polyamic acid, it is preferable to recover the obtained imidized polymer and redissolve it with an organic solvent by the following means to form the liquid crystal aligning agent of the present invention.

The solution of the polyimide obtained as described above can be poured into a poor solvent while sufficiently stirring, thereby allowing a polymer to be precipitated. The polymer is precipitated several times, washed with a poor solvent, and dried at normal temperature or heated to obtain a purified polymer powder.

The poor solvent is not particularly limited, and examples thereof include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene, and methanol, ethanol, 2-propanol, and acetone are preferable.

< preparation of polyimide precursor-polyamic acid ester >

The polyamic acid ester used as the polyimide precursor in the present invention can be produced by the following production method of (i), (ii), or (iii).

(i) Case of production from Polyamic acid

The polyamic acid ester can be produced by esterifying the polyamic acid produced as described above. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at-20 to 150 ℃, preferably 0 to 50 ℃, for 30 minutes to 24 hours, preferably 1 to 4 hours.

The esterification agent is preferably one which can be easily removed by purification, and examples thereof include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dineopentylbutyl acetal, N-dimethylformamide di-tert-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, and 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholine hydrochloride. The amount of the esterifying agent to be added is preferably 2 to 6 molar equivalents based on 1 mole of the repeating unit of the polyamic acid.

Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and 1, 3-dimethyl-imidazolidinone. When the polyimide precursor has high solubility in the solvent, a solvent represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulae [ D-1] to [ D-3] can be used.

Formula [ D-1]In (D)¹Represents an alkyl group having 1 to 3 carbon atoms of the formula [ D-2 ]]In (D)²Represents an alkyl group having 1 to 3 carbon atoms, formula [ D-3]]In (D)³Represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Further, even if the solvent is a solvent which does not dissolve the polyimide precursor, the solvent may be mixed with the polyimide precursor and used within a range where the polyimide precursor to be produced is not precipitated. In addition, the solvent is preferably dehydrated and dried because moisture in the solvent interferes with the polymerization reaction and further causes hydrolysis of the polyimide precursor to be produced.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ -butyrolactone from the viewpoint of the solubility of the polymer, and 1 kind or 2 or more kinds mixed may be used. The concentration in the production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, because precipitation of the polymer hardly occurs and a high molecular weight product is easily obtained.

(ii) Produced by reaction of a tetracarboxylic acid diester dichloride with a diamine

The polyamic acid ester can be made from a tetracarboxylic acid diester dichloride and a diamine.

Specifically, the reaction can be carried out by reacting a tetracarboxylic acid diester dichloride with a diamine in the presence of a base and an organic solvent at-20 to 150 ℃, preferably 0 to 50 ℃ for 30 minutes to 24 hours, preferably 1 to 4 hours.

Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the base, and pyridine is preferred for mildly proceeding the reaction. The amount of the base to be added is preferably 2 to 4 times by mol based on the tetracarboxylic acid diester dichloride, from the viewpoint of easy removal and easy availability of a high molecular weight product.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ -butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and 1 kind or 2 or more kinds mixed may be used. The polymer concentration during production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, because precipitation of the polymer is not likely to occur and a high molecular weight product is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for producing the polyamic acid ester is preferably dehydrated as much as possible, and is preferably kept from being mixed with an external gas in a nitrogen atmosphere.

(iii) From tetracarboxylic diesters and diamines

The polyamic acid ester can be produced by polycondensing a tetracarboxylic acid diester with a diamine.

Specifically, the tetracarboxylic acid diester can be produced by reacting the tetracarboxylic acid diester with a diamine in the presence of a condensing agent, a base and an organic solvent at 0 to 150 ℃, preferably 0 to 100 ℃, for 30 minutes to 24 hours, preferably 3 to 15 hours.

Among the above condensing agents, there can be used: triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N ' -carbonyldiimidazole, dimethoxy-1, 3, 5-triazinylmethyl morpholinium, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N ' -tetramethyluronium hexafluorophosphate, diphenyl (2, 3-dihydro-2-thio-3-benzoxazolyl) phosphonate, and the like. The amount of the condensing agent to be added is preferably 2 to 3 times by mol based on the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be added is preferably 2 to 4 times by mole relative to the diamine component, from the viewpoint of easy removal and easy availability of a high molecular weight material.

In addition, in the above reaction, lewis acid is added as an additive, so that the reaction efficiently proceeds. As the lewis acid, lithium halide such as lithium chloride or lithium bromide is preferable. The amount of the Lewis acid added is preferably 0 to 1.0 mol per mol of the diamine component.

Among the above-mentioned 3 methods for producing polyamic acid esters, a polyamic acid ester having a high molecular weight can be obtained, and therefore, the method for producing the above-mentioned (i) or (ii) is particularly preferable.

The solution of the polyamic acid ester obtained as described above can be poured into a poor solvent while sufficiently stirring, thereby allowing the polymer to precipitate. The polyamic acid ester may be precipitated several times, washed with a poor solvent, and dried at room temperature or heated to obtain a purified polyamic acid ester powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

In the above-mentioned production method, the diamine represented by the formula (1) can be used for producing the polymer of the present invention. In this case, as the diamine, a substance other than the substance represented by the formula (1) can be used. Specific examples thereof include the following diamines: a diamine having 2 amino groups bonded to the structure of formula (2) described in item 4 of International publication No. 2015/119168, and a diamine having 2 amino groups bonded to the structures of formulae (Y-1) to (Y-97) and formulae (Y-101) to (Y-118) described in items 8 to 12; a diamine of the formula (2) described in item 6 of International publication No. 2013/008906; a diamine of the formula (1) described in item 8 of International publication No. 2015/122413; a diamine having 2 amino groups bonded to the structure of formula (3) described in 8 of International publication No. 2015/060360; a diamine of the formula (1) described in 8 of Japanese laid-open patent publication No. 2012-173514; diamines of the formulae (A) to (F) described in 9 of International publication No. 2010-050523; and the like.

The polymer of the present invention thus obtained can be used not only as a coating material but also as an insulating film, a film substrate, a liquid crystal alignment film, a protective film, and the like.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited thereto.

The structures of the diamine compounds used in the examples are shown below.

< diamine Compound >

DA-1 to DA-8 and DA-10 to DA-15 are novel compounds which are not disclosed in the literature, etc., and the synthesis methods thereof are described in detail in the following synthesis examples 1 to 14.

DA-9 was synthesized by a synthesis method described in patent document (WO 2017-057854).

Abbreviations of the organic solvents used in examples and the like are as follows.

NMP: n-methyl-2-pyrrolidone.

BCS: butyl cellosolve.

THF: tetrahydrofuran.

DMF: n, N-dimethylformamide.

CH₂Cl₂: dichloromethane.

CHCl₃: chloroform.

MeOH: methanol.

EtOH: and (3) ethanol.

IPA: and (3) isopropanol.

1, 3-DMCBDA: 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride

＜¹Measurement of HNMR

The device comprises the following steps: fourier transform superconducting Nuclear magnetic resonance apparatus (FT-NMR) "INOVA-400" (manufactured by Varian) 400 MHz.

Solvent: deuterated chloroform (CDCl)₃) Or deuterated N, N-dimethyl sulfoxide ([ D ]₆]-DMSO)。

Standard substance: tetramethylsilane (TMS).

(Synthesis example 1)

Synthesis of [ DA-1 ]:

in a 3L four-necked flask, 4- [ (4-aminophenoxy) methoxy ] aniline (230.0g, 999mmol) and THF (1600g) were placed, and di-tert-butyl dicarbonate (218.0g, 999mmol) was added dropwise to the flask in a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained residue was separated by silica gel column chromatography (ethyl acetate: hexane: 1 by volume), whereby [ DA-1-1]158.0g was obtained.

[ DA-1-1] (132.2g, 400mmol) and NMP (1300g) were put in a 3L four-necked flask, and 1,3-DMCBDA (40.4g, 180mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (85.5g, 1081mmol) and acetic anhydride (55.2g, 540mmol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (5L), and the precipitate was filtered off. MeOH (2L) was added to the resulting crude product, followed by reslurry washing at room temperature to obtain 180.1g of [ DA-1-2 ].

[ DA-1-2] was put into a 3L four-necked flask](169.8g、200mmol)、CH₂Cl₂(2500g) Trifluoroacetic acid (204.1g, 1000mmol) was added dropwise to the water bath, followed by stirring at room temperature. After the reaction was completed, the reaction solution was concentrated, and pure water (3L) was added to the obtained crude product to neutralize it with triethylamine. The precipitate was filtered, and THF (500g) and MeOH (700g) were added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-1]](white solid) 106.0 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-1] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.35-7.37(d,4H),7.21-7.23(d,4H),6.78-6.80(d,4H),6.50-6.52(d,4H),5.71(s,4H),4.79(s,4H),3.54(s,2H),1.38(s,6H)

(Synthesis example 2)

Synthesis of [ DA-2 ]:

4- [3- (4-aminophenoxy) propoxy ] aniline (70.0g, 271mmol) and THF (500g) were placed in a 3L four-necked flask, and di-tert-butyl dicarbonate (59.1g, 271mmol) was added dropwise to a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained residue was separated by silica gel column chromatography (ethyl acetate: hexane: 1 by volume), whereby 46.4g of [ DA-2-1] was obtained.

[ DA-2-1] (46.4g, 129mmol) and NMP (460g) were put in a 3L four-necked flask, and 1,3-DMCBDA (14.5g, 65mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (30.7g, 388mmol) and acetic anhydride (19.8g, 194mmol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (3L), and the precipitate was filtered off. MeOH (400ml) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-2-2]41.1 g.

[ DA-2] was put into a 3L four-necked flask](41.1g、45mmol)、CH₂Cl₂(600g) Trifluoroacetic acid (46.4g, 454mmol) was added dropwise to the water bath, followed by stirring at room temperature. After the reaction, the reaction mixture was concentrated, and pure water (2L) was added to the obtained crude product to neutralize it with triethylamine. The precipitate was filtered, EtOH (100g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-2]](white solid) 25.3 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-2] aimed at the obtained solid was]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.30-7.33(d,4H),7.08-7.11(d,4H),6.66-6.70(d,4H),6.48-6.52(d,4H),4.62(s,2H),4.15-4.18(t,4H),3.98-4.01(t,4H),3.51(s,2H),2.10-2.16(t,4H),1.38(s,6H)

(Synthesis example 3)

Synthesis of [ DA-3 ]:

in a 3L four-necked flask, 4- [6- (4-aminophenoxy) hexyloxy ] aniline (90.0g, 300mmol) and THF (600g) were placed, and di-tert-butyl dicarbonate (65.4g, 300mmol) was added dropwise to the flask in a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained residue was separated by silica gel column chromatography (ethyl acetate: hexane: 1 by volume), whereby 48.0g of [ DA-3-1] was obtained.

[ DA-3-1] (48.0g, 120mmol) and NMP (480g) were put into a 3L four-necked flask, and 1,3-DMCBDA (13.4g, 60mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (28.4g, 360mmol) and acetic anhydride (18.4g, 180mmol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (3L), and the precipitate was filtered off. MeOH (400ml) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-3-2]42.5 g.

[ DA-3-2] was put into a 3L four-necked flask](42.5g、43mmol)、CH₂Cl₂(640g) Trifluoroacetic acid (43.9g, 430mmol) was added dropwise to the water bath, followed by stirring at room temperature. After the reaction, the reaction mixture was concentrated, and pure water (2L) was added to the obtained crude product to neutralize it with triethylamine. The precipitate was filtered, MeOH (100g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-3]](purple solid) 26.3 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-3] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.29-7.31(d,4H),7.06-7.08(d,4H),6.63-6.65(d,4H),6.48-6.50(d,4H),4.59(s,4H),4.01-4.04(t,4H),3.80-3.84(t,4H),3.52(s,2H),1.74-1.76(t,4H),1.66-1.70(t,4H),1.46-1.48(m,8H),1.38(s,6H)

(Synthesis example 4)

Synthesis of [ DA-4 ]:

into a 2L four-necked flask, N-Boc-2- (4-aminophenyl) ethanol (158.7g, 669mmol), triethylamine (135.4g, 1338mmol) and THF (1100g) were charged, and ethanesulfonyl chloride (128.9g, 1003mmol) was added dropwise to the flask in a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (3L) and extracted with pure water (1L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain 224.2g of [ DA-4-1 ].

[ DA-4-1] (217.3g, 660mmol), 4-nitrophenol (101.0g, 726mmol), potassium carbonate (136.8g, 990mmol), and NMP (1200g) were put in a 3L four-necked flask, and stirred at 80 ℃. After completion of the reaction, the reaction system was poured into ethyl acetate (2L) and neutralized with 1N-hydrochloric acid aqueous solution. The aqueous layer was removed, and the organic layer was washed with pure water (2L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to remove the solvent, IPA (400g) was added, and reslurrying and washing were performed at room temperature to obtain 164.8g of [ DA-4-2 ].

[ DA-4-2] (84.3g, 226mmol), 6N-hydrochloric acid aqueous solution (200g), and ethyl acetate (600g) were put in a 2L four-necked flask, and stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (1.2L) and neutralized with a 1N-aqueous sodium hydroxide solution. The aqueous layer was removed, and the organic layer was washed with pure water (2L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain 60.8g of [ DA-4-3 ].

[ DA-4-3] (60.8g, 235mmol) and NMP (600g) were put in a 2L four-necked flask, and 1,3-DMCBDA (24.8g, 111mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (55.8g, 705mmol) and acetic anhydride (35.9g, 352mmol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (3L), and the precipitate was filtered off. EtOH (1000g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-4-4]79.1 g.

A3L four-necked flask was charged with [ DA-4]](79.0g, 112mmol) and DMF (800g) were replaced with nitrogen, and then 5 wt% Pd/C (7.9g) was added thereto, and the mixture was replaced with hydrogen and stirred at room temperature. After completion of the reaction, the reaction mixture was filtered through a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation by a rotary evaporator, and ethyl acetate (1) was added500g) Repulping and washing at room temperature to obtain [ DA-4]](white solid) 69.9 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-4] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.46-7.48(d,4H),7.33-7.35(d,4H),6.65-6.68(d,4H),6.49-6.51(d,4H),4.61(s,4H),4.07-4.10(t,4H),3.54(s,2H),3.02-3.05(t,4H),1.39(s,6H)

(Synthesis example 5)

Synthesis of [ DA-5 ]:

[ DA-4-2] (80.6g, 216mmol), THF (300g) and EtOH (100g) were put into a 1L four-necked flask, and after replacement with nitrogen, 5 wt% Pd/C (8.0g) was added thereto, and hydrogen replacement was carried out, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was filtered through a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain 73.9g of [ DA-5-1 ].

[ DA-5-1] (73.9g, 225mmol) and NMP (700g) were put in a 2L four-necked flask, and 1,3-DMCBDA (23.7g, 106mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (53.4g, 675mmol) and acetic anhydride (34.5g, 338mol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (3L), and the precipitate was filtered off. EtOH (1000g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-5-2]85.4 g.

A2L four-necked flask was charged with [ DA-5-2]](85.4g, 101mmol), 6N-hydrochloric acid aqueous solution (200g), and ethyl acetate (800g) were stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (1.2L) and neutralized with triethylamine. The precipitate was filtered off, ethyl acetate (1500g) was added thereto, and repulping and washing were performed at room temperature to obtain [ DA-5]]61.1 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-5] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.29-7.31(d,4H),7.05-7.08(d,4H),6.97-6.99(d,4H),6.51-6.53(d,4H),4.90(s,4H),4.11-4.14(t,4H),3.51(s,2H),2.86-2.89(t,4H),1.37(s,6H)

(Synthesis example 6)

Synthesis of [ DA-6 ]:

into a 2L four-necked flask, 3- (4-tert-butoxycarbonylaminophenyl) propanol (237.3g, 944mmol), triethylamine (190.0g, 1888mmol) and THF (1000g) were charged, and ethanesulfonyl chloride (182.0g, 1416mmol) was added dropwise to the flask over a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (2L) and extracted with pure water (1L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain [ DA-6-1]324.2 g.

[ DA-6-1] (324.2g, 944mmol), 4-nitrophenol (150.0g, 1078mmol), potassium carbonate (203.0g, 1470mmol) and NMP (1700g) were put in a 3L four-necked flask, and stirred at 80 ℃. After completion of the reaction, the reaction system was poured into ethyl acetate (4L) and neutralized with 1N-hydrochloric acid aqueous solution. The aqueous layer was removed, and the organic layer was washed with pure water (2L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to remove IPA (2000g), followed by reslurry washing at room temperature to obtain 173.4g of [ DA-6-2 ].

[ DA-6-2] (86.7g, 233mmol), a 6N-hydrochloric acid aqueous solution (180g), and ethyl acetate (700g) were put in a 2L four-necked flask, and stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (1L) and neutralized with a 1N-sodium hydroxide aqueous solution. The aqueous layer was removed, and the organic layer was washed with pure water (2L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration and drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain 62.6g of [ DA-6-3 ].

[ DA-6-3] (62.6g, 230mmol) and NMP (900g) were put in a 2L four-necked flask, and 1,3-DMCBDA (25.5g, 114mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (54.5g, 690mmol) and acetic anhydride (35.2g, 345mmol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (4L), and the precipitate was filtered off. MeOH (500g) was added to the resulting crude product, followed by reslurrying and washing at room temperature, thereby obtaining [ DA-6-4]82.0 g.

A5L four-necked flask was charged with [ DA-6-4]](80.0g, 109mmol) and DMF (3200g) were replaced with nitrogen, and then 5 wt% Pd/C (8.0g) was added thereto, and the mixture was replaced with hydrogen, followed by stirring at 60 ℃. After completion of the reaction, the reaction mixture was filtered through a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to remove the solvent, ethyl acetate (1000g) was added thereto, and repulping and washing were carried out at room temperature to obtain [ DA-6]](purple solid) 59.1 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-6] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.38-7.40(d,4H),7.31-7.33(d,4H),6.65-6.67(d,4H),6.49-6.51(d,4H),4.60(d,4H),3.83-3.86(t,4H),3.54(s,2H),2.73-2.80(t,4H),1.97-2.01(t,4H),1.39(s,6H)

(Synthesis example 7)

Synthesis of [ DA-7 ]:

[ DA-6-2] (86.7g, 233mmol), THF (350g), and EtOH (90g) were put into a 1L four-necked flask, and after replacement with nitrogen, 5 wt% Pd/C (8.7g) was added thereto, and hydrogen replacement was performed, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was filtered through a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation by a rotary evaporator to thereby obtain 65.8g of [ DA-7-1 ].

[ DA-7-1] (65.8g, 192mmol) and NMP (700g) were put in a 2L four-necked flask, and 1,3-DMCBDA (21.4g, 96mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (45.6g, 576mmol) and acetic anhydride (29.8g, 292mol) were put into the reaction solution, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (3L), and the precipitate was filtered off. MeOH (1000g) was added to the resulting crude product, followed by reslurry washing at room temperature to obtain [ DA-7-2]83.0 g.

A2L four-necked flask was charged with [ DA-7-2]](83.0g, 96mmol), 6N-hydrochloric acid aqueous solution (170g), and ethyl acetate (700g) were stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (1L) and neutralized with triethylamine. The precipitate was filtered off, ethyl acetate (500g) was added thereto, and repulping and washing were performed at room temperature to obtain [ DA-7]]25.2 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-7] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.29-7.32(d,4H),7.05-7.07(d,4H),6.87-6.89(d,4H),6.49-6.51(d,4H),4.86(d,4H),3.97-4.00(t,4H),3.52(s,2H),2.56-2.60(t,4H),1.93-1.97(t,4H),1.38(s,6H)

(Synthesis example 8)

Synthesis of [ DA-8 ]:

2- (4-Nitrophenyl) ethylamine hydrochloride (50.0g, 247mmol), triethylamine (27.5g, 271mmol) and THF (500g) were put into a 1L four-necked flask, and 1,3-DMCBDA (27.1g, 121mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. After completion of the reaction, the reaction system was poured into pure water (1.5L), and the precipitate was filtered off to obtain 67.2g of [ DA-8-1 ].

[ DA-8-1] (67.2g, 121mmol) and acetic acid (400g) were put in a 1L four-necked flask, and stirred at 100 ℃. After completion of the reaction, the reaction system was poured into pure water (1.5L), and the precipitate was filtered off. MeOH (60g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-8-2]30.4 g.

A1L four-necked flask was charged with [ DA-8-2]](30.4g, 58mmol) and DMF (450g) were replaced with nitrogen, and then 5 wt% Pd/C (3.0g) was added thereto, and the mixture was replaced with hydrogen and stirred at room temperature. After completion of the reaction, the reaction mixture was filtered through a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was poured into pure water (3L), and the precipitate was filtered off. MeOH (80g) was added to the crude product obtained, followed by reslurrying and washing at room temperature to obtain [ DA-8]](white solid) 25.9 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-8] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ6.82-6.84(d,4H),6.46-6.48(d,4H),4.91(s,4H),3.50-3.66(m,4H),2.96(s,2H),2.66-2.73(t,4H),0.94(d,1H)

(Synthesis example 9)

Synthesis of [ DA-10 ]:

2- (4-Nitrophenyl) ethylamine hydrochloride (25.0g, 123mmol), triethylamine (14.2g, 140mmol) and THF (250g) were charged in a 1L four-necked flask, and 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (11.7g, 60mmol) was added to a water bath and then stirred at room temperature for 6 hours. After completion of the reaction, the reaction system was poured into pure water (2L), and the precipitate was filtered off. IPA (500g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain 21.8g of [ DA-10-1 ].

[ DA-10-1] (21.8g, 41mmol), pyridine (28.5g, 360mmol), acetic anhydride (20.1g, 197mol) and NMP (225g) were put into a 1L four-necked flask, and stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (2L), and the precipitate was filtered off. MeOH (400g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-10-2]19.3 g.

A1L four-necked flask was charged with [ DA-10-2]](19.3g, 39mmol) and DMF (400g) were replaced with nitrogen, and then 5 wt% Pd/C (2.0g) was added thereto, and the mixture was replaced with hydrogen and stirred at room temperature. After the reaction, the reaction mixture was filtered through a 0.45 μm membrane filterFiltration was performed to remove Pd/C. The obtained filtrate was poured into pure water (3L), and the precipitate was filtered off. MeOH (300g) was added to the resulting crude product, followed by reslurry washing at room temperature to obtain [ DA-10]](white solid) 15.2 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-10] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ6.81-6.83(d,4H),6.46-6.48(d,4H),4.90(s,4H),3.54-3.57(t,4H),3.08(s,2H),2.63-2.67(t,4H)

(Synthesis example 10)

Synthesis of [ DA-11 ]:

into a 1L four-necked flask, N' -bis [2- (4-aminophenyl) ethyl group was charged]Urea (134.4g, 450mmol) and DMF (650g) were added dropwise to a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction mixture was concentrated, and pure water (1.5L) was added to filter out the precipitate. Adding CHCl into the obtained crude product₃(1.5L), the organic layer was washed with 10 wt% aqueous acetic acid (1.5L). Further, the organic layer was neutralized with triethylamine, washed with pure water (2L), and then concentrated to obtain [ DA-11-1]50.8g。

[ DA-11-1] (49.0g, 123mmol) and NMP (500g) were put in a 2L four-necked flask, and 1,3-DMCBDA (13.5g, 60mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (29.4g, 369mmol) and acetic anhydride (18.8g, 185mol) were put into the reaction solution, and the mixture was stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (2.5L), and the precipitate was filtered off. Then, THF (800g) was added to the obtained crude product to completely dissolve the product, followed by concentration at 40 ℃ until a solid precipitated, MeOH (200g) was added, and reslurry washing was performed at room temperature to obtain 47.7g of [ DA-11-2 ].

A1L four-necked flask was charged with [ DA-11-2]](47.7g、48mmol)、CHCl₃(480g) Trifluoroacetic acid (55.7g, 484mmol) was added dropwise to a water bath, followed by stirring at 50 ℃. After completion of the reaction, the reaction mixture was poured into hexane (500g), and the precipitate was filtered off. Subsequently, MeOH (500g) was added to the crude product, neutralized with triethylamine, and the precipitate was filtered off. Subsequently, DMF (300g) was added to the crude product obtained, the mixture was heated to 60 ℃ to completely dissolve the DMF, the mixture was concentrated at 40 ℃ until a solid precipitated, THF (600g) was added, and reslurry washing was carried out at room temperature to obtain [ DA-11]](white solid) 25.2 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-11] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.32-7.38(m,8H),6.83-6.85(d,4H),6.48-6.50(d,4H),5.92-5.95(t,2H),5.81-5.84(t,2H),4.87(s,4H),3.55(s,2H),3.24-3.29(m,4H),3.10-3.15(m,4H),2.72-2.76(m,4H),2.47-2.51(m,4H),1.39(s,6H)

(Synthesis example 11)

Synthesis of [ DA-12 ]:

a500 mL four-necked flask was charged with 1- (4-nitrophenyl) -4-piperidinamine (39.0g, 116mmol) and NMP (400g), and 1,3-DMCBDA (12.8g, 47mmol) was added to the flask in a water bath, followed by stirring at 50 ℃ for 6 hours. Subsequently, pyridine (27.6g, 349mmol) and acetic anhydride (17.8g, 175mol) were put into the reaction solution, and stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (2L), and the precipitate was filtered off. Next, MeOH (250g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-12-1]32.1 g.

A2L four-necked flask was charged with [ DA-12-1]](32.1g, 51mmol) and DMF (960g) were replaced with nitrogen, and then 5 wt% Pd/C (3.2g) was added thereto, and the mixture was replaced with hydrogen, followed by stirring at 50 ℃. After completion of the reaction, the reaction mixture was filtered, and 2N-hydrochloric acid aqueous solution (1L) was added to the obtained residue, followed by filtration through a 0.45 μm membrane filter to remove Pd/C. To the obtained filtrate, triethylamine was added until the solution became basic, and the precipitate was filtered off. Further, MeOH (100g) was added to the crude product obtained, and the reaction was carried out at room temperatureRepulping and cleaning to obtain [ DA-12]](carmine solid) 22.1 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that the obtained solid was the target [ DA-12]]。

¹H NMR(400MHz,[D₆]-DMSO):δ6.71-6.73(m,4H),6.47-6.50(m,4H),4.68(s,4H),3.95-4.01(m,2H),3.42-3.45(d,4H),3.13(s,2H),2.51-2.59(m,4H),2.39-2.50(m,4H),1.62-1.71(q,4H),1.17(s,6H)

(Synthesis example 12)

Synthesis of [ DA-13 ]:

4-amino-1-tert-butoxycarbonylpiperidine (70.0g, 350mmol) and NMP (700g) were put in a 2L four-necked flask, and 1,3-DMCBDA (38.4g, 171mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (82.9g, 1049mmol) and acetic anhydride (53.5g, 524mol) were put into the reaction solution, and the mixture was stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (3.5L), and the precipitate was filtered off. Next, MeOH (300g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-13-1]92.0 g.

A2L four-necked flask was charged with [ DA-13-1]](92.0g、170mmol)、CHCl₃(920g) Trifluoroacetic acid (193.3g, 1700mol) was added dropwise to the water bath, followed by stirring at 50 ℃. After completion of the reaction, the precipitate was filtered off, ethyl acetate (300g) was added to the obtained crude product, followed by reslurrying and washing at room temperature to obtain [ DA-13-2]]97.8g。

[ DA-13-2] (40.0g, 65mmol), 2- (4-nitrophenyl) ethyl bromide (32.8g, 143mmol), potassium carbonate (35.9g, 260mmol) and NMP (400g) were put in a 1L four-necked flask, and the mixture was stirred at 60 ℃. After completion of the reaction, the reaction system was poured into pure water (2L), and the precipitate was filtered off. MeOH (200g) was added to the resulting crude product, followed by reslurry washing at 60 ℃ to obtain 27.5g of [ DA-13-3 ].

[ DA-13-3] was put into a 3L four-necked flask](29.3g, 43mmol) and DMF (900g) were replaced with nitrogen5 wt% Pd/C (2.9g) was added to conduct hydrogen substitution, and stirring was conducted at 60 ℃. After completion of the reaction, the reaction mixture was concentrated, and 2N-hydrochloric acid aqueous solution (1L) was added to the crude product obtained, followed by filtration through a 0.45 μm membrane filter to remove Pd/C. To the obtained filtrate, triethylamine was added until the solution became basic, and the precipitate was filtered off. Further, MeOH (100g) was added to the resulting crude product, followed by reslurry washing at room temperature to obtain [ DA-13]](skin color solids) 8.7 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-13] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ6.84-6.86(d,4H),6.46-6.48(d,4H),4.82(s,4H),3.83-3.89(m,2H),3.10(s,2H),2.99-3.01(d,4H),2.49-2.56(m,4H),2.39-2.43(m,4H),2.26-2.32(m,4H),1.94-1.99(t,4H),1.52-1.61(q,4H),1.14(s,6H)

(Synthesis example 13)

Synthesis of [ DA-14 ]:

a500 mL four-necked flask was charged with tert-butyl 4- (4-aminophenyl) piperidine-1-carboxylate (22.8g, 82mmol) and NMP (230g), and 1,3-DMCBDA (8.9g, 40mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (39.1g, 494mmol) and acetic anhydride (25.2g, 247mol) were put into the reaction solution, and stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (1.5L), and the precipitate was filtered off. Next, MeOH (100g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-14-1]28.5 g.

A500 mL four-necked flask was charged with [ DA-14-1]](28.5g、39mmol)、CHCl₃(290g) Trifluoroacetic acid (43.9g, 385mol) was added dropwise to the water bath, followed by stirring at 50 ℃. After completion of the reaction, the precipitate was filtered off, MeOH (150g) was added to the resulting crude product, and reslurrying and washing were carried out at room temperature to obtain [ DA-14-2]]29.2g。

[ DA-14-2] (28.5g, 37mmol), 2- (4-nitrophenyl) ethyl bromide (29.5g, 111mmol), triethylamine (30.0g, 296mmol) and NMP (290g) were put in a 1L four-necked flask, and the mixture was stirred at 80 ℃. After completion of the reaction, the reaction system was poured into pure water (2.5L), and the precipitate was filtered off. MeOH (250g) was added to the resulting crude product, followed by reslurry washing at 60 ℃ to obtain 26.1g of [ DA-14-3 ].

A3L four-necked flask was charged with [ DA-14-3]](26.1g, 31mmol) and DMF (800g) were replaced with nitrogen, and then 5 wt% Pd/C (2.6g) was added thereto, and the mixture was replaced with hydrogen, followed by stirring at 80 ℃. After completion of the reaction, the reaction mixture was concentrated, and 2N-hydrochloric acid aqueous solution (1L) was added to the crude product obtained, followed by filtration through a 0.45 μm membrane filter to remove Pd/C. To the obtained filtrate, triethylamine was added until the solution became basic, and the precipitate was filtered off. Further, MeOH (100g) was added to the resulting crude product, followed by reslurry washing at room temperature to obtain [ DA-14]](skin color solids) 12.3 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-14] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.38-7.43(d,4H),7.31-7.33(d,4H),6.86-6.88(d,4H),6.47-6.49(d,4H),4.83(s,4H),3.53(s,2H),3.04-3.06(d,4H),2.52-2.58(m,6H),2.45-2.50(m,4H),2.03-2.08(t,4H),1.67-1.77(m,8H),1.39(s,6H)

(Synthesis example 14)

Synthesis of [ DA-15 ]:

tert-butyl 4- (4-aminophenyl) piperazine-1-carboxylate (33.2g, 120mmol) and NMP (330g) were put in a 1L four-necked flask, and 1,3-DMCBDA (13.1g, 59mmol) was added to the flask in a water bath, followed by stirring at room temperature for 6 hours. Subsequently, pyridine (28.4g, 359mmol) and acetic anhydride (18.3g, 180mol) were put into the reaction solution, and the mixture was stirred at 50 ℃. After completion of the reaction, the reaction system was poured into pure water (2L), and the precipitate was filtered off. Next, MeOH (150g) was added to the resulting crude product, followed by reslurrying and washing at room temperature to obtain [ DA-15-1]40.7 g.

Put into a 2L four-neck flask[ DA-15-1]](40.7g、55mmol)、CHCl₃(400g) Trifluoroacetic acid (62.6g, 548mol) was added dropwise to the water bath, followed by stirring at 50 ℃. After completion of the reaction, the precipitate was filtered off, THF (200g) was added to the obtained crude product, followed by reslurrying and washing at 50 ℃ to obtain [ DA-15-2]]21.8g。

[ DA-15-2] (21.8g, 28mmol), 2- (4-nitrophenyl) ethyl bromide (14.3g, 62mmol), triethylamine (11.4g, 113mmol) and NMP (220g) were put in a 500mL four-necked flask, and the mixture was stirred at 80 ℃. After completion of the reaction, the reaction system was poured into pure water (1L), and the precipitate was filtered off. MeOH (200g) was added to the resulting crude product, followed by reslurry washing at 60 ℃ to obtain 17.9g of [ DA-15-3 ].

A3L four-necked flask was charged with [ DA-14-3]](17.9g, 21mmol) and DMF (540g) were replaced with nitrogen, and then 5 wt% Pd/C (1.8g) was added thereto, and the mixture was replaced with hydrogen, followed by stirring at 80 ℃. After completion of the reaction, the reaction mixture was concentrated, and 2N-hydrochloric acid aqueous solution (500mL) was added to the crude product obtained, followed by filtration through a 0.45 μm membrane filter to remove Pd/C. To the obtained filtrate, triethylamine was added until the solution became basic, and the precipitate was filtered off. Further, MeOH (50g) was added to the resulting crude product, followed by reslurry washing at 60 ℃ to obtain [ DA-15]](skin color solids) 5.7 g. Of the object¹The results of H-NMR are shown below. From the results, it was confirmed that [ DA-15] aimed at the obtained solid was obtained]。

¹H NMR(400MHz,[D₆]-DMSO):δ7.19-7.22(d,4H),7.04-7.06(d,4H),6.87-6.89(d,4H),6.47-6.49(d,4H),4.84(s,4H),3.48(s,2H),3.34(s,6H),3.21(s,8H),2.58(s,10H),1.36(s,6H)

< measurement of saturated solubility to NMP at room temperature of diamine Compound >

(example 1)

To NMP (2g) heated to 60 ℃ was added the diamine compound [ DA-1] until a dissolved residue was formed, and stirring was carried out at 60 ℃ for 1 hour. After heating, the mixture was naturally cooled at room temperature for 6 hours to remove the precipitate, thereby preparing a saturated NMP solution of [ DA-1] at room temperature. Next, a 1 wt% NMP solution of [ DA-1] was prepared as a standard, and the peak area was measured by HPLC. Finally, NMP (39g) was added to the prepared saturated solution (1g), and the peak area was measured to calculate the saturated solubility of [ DA-1] for NMP at room temperature.

(examples 2 to 9, comparative examples 1 to 2)

As shown in Table 1, examples 2 to 9 were also calculated by the same method as in example 1. In addition, comparative examples 1 to 2 were also calculated by the same method.

[ Table 1]

As shown in Table 1, it was confirmed that the diamine compounds (DA-1 to DA-8, DA-11) of examples 1 to 9 of the present invention exhibited better solubility in NMP at room temperature than the diamine compound (DA-9) of comparative example 1. In addition, it was confirmed that the diamine compound (DA-8) of example 8 exhibited a better solubility at room temperature in terms of saturation with NMP than the diamine compound (DA-10) of comparative example 2. From the above, it is suggested that the solubility to NMP can be improved by making the diamine compound have the structure of the present invention.

< determination of the molecular weight of the Polymer >

The molecular weights of the polyimide, polyamic acid, and polyamic acid ester in the examples were measured as follows using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) manufactured by Shodex corporation and columns (KD-803 and KD-805) manufactured by Shodex corporation.

Column temperature: 50 deg.C

Eluent: DMF (as additive, lithium bromide-hydrate (LiBr. H)₂O) is 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) is 30mmol/L, THF is 10mL/L)

Flow rate: 1.0 mL/min

Standard sample for standard curve preparation: TSK standard polyethylene oxide (molecular weight about 900000, 150000, 100000, 30000, manufactured by Tosoh corporation) and polyethylene glycol (molecular weight about 12000, 4000, 1000, manufactured by Polymer Laboratories Ltd.).

Polymerization example 1

A polyamic acid-polyimide polymer solution (PI-1) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.64g (1.0mmol) of DA-1 in NMP (7.48g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 29500.

(polymerization example 2)

A polyamic acid-polyimide polymer solution (PI-2) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.70g (1.0mmol) of DA-2 in NMP (7.98g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 30000.

(polymerization example 3)

A polyamic acid-polyimide polymer solution (PI-3) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.78g (1.0mmol) of DA-3 in NMP (8.74g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 32000.

Polymerization example 4

A polyamic acid-polyimide polymer solution (PI-4) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.64g (1.0mmol) of DA-4 in NMP (7.44g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 14800.

Polymerization example 5

A polyamic acid-polyimide polymer solution (PI-5) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.64g (1.0mmol) of DA-5 in NMP (7.44g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 9900.

Polymerization example 6

A polyamic acid-polyimide polymer solution (PI-6) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.67g (1.0mmol) of DA-6 in NMP (7.69g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 8700.

Polymerization example 7

A polyamic acid-polyimide polymer solution (PI-7) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.67g (1.0mmol) of DA-7 in NMP (7.69g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 169900.

Polymerization example 8

A polyamic acid-polyimide polymerization solution (PI-8) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.46g (1.0mmol) of DA-8 in NMP (5.78g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 8900.

Polymerization example 9

A polyamic acid-polyimide polymerization solution (PI-9) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.40g (1.0mmol) of DA-9 in NMP (5.28g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 13600.

Polymerization example 10

A polyamic acid-polyimide polymer solution (PI-10) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.43g (1.0mmol) of DA-10 in NMP (5.53g) at room temperature for 16 hours. The polyamic acid-polyimide has a number average molecular weight of about 8500.

Polymerization example 11

A polyamic acid-polyimide polymer solution (PI-11) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.78g (1.0mmol) of DA-11 in NMP (8.71g) at room temperature for 16 hours. The polyamic acid-polyimide had a number average molecular weight of about 9600.

Polymerization example 12

A polyamic acid-polyimide polymer solution (PI-12) was prepared by reacting 0.18g (0.93mol) of CBDA and 0.57g (1.0mmol) of DA-12 in NMP (6.78g) at room temperature for 16 hours. The polyamic acid-polyimide has a number average molecular weight of about 11200.

< determination of solubility of Polyamic acid-polyimide >

(example 10)

BCS was added to 3g of the polyamic acid-polyimide polymerization solution (PI-1) and stirred to prepare a solution (A-1) such that the polyamic acid-polyimide was 6 mass%, NMP was 54 mass%, and BCS was 40 mass%, and the solubility of the polyamic acid-polyimide was confirmed at room temperature and at freezing (-20 ℃).

(examples 11 to 19 and comparative examples 3 to 4)

As shown in Table 2, the solubility of examples 11 to 19 was confirmed by the same method as in example 10. In addition, the solubility was confirmed in comparative examples 3 to 4 in the same manner. The solubility is expressed by the following standard.

○ no turbidity, precipitate, gelation

△ slight cloudiness

X: turbidity, precipitate, gelation

[ Table 2]

As shown in Table 2, it was confirmed that the polyamic acid-polyimide solutions obtained by polymerizing the diamine compounds (DA-1 to DA-8, DA-11 to DA-12) of the present invention and diluting with BCS as a poor solvent in examples 10 to 19 exhibited good solubility without turbidity, precipitates, gelation, and the like in the varnish at room temperature and at freezing (-20 ℃ C.). On the other hand, it was confirmed that the polyamic acid-polyimide solutions of comparative examples 3 and 4 were turbid, precipitated, and gelled in the varnish at room temperature and in the frozen state (-20 ℃ C.). From the above, it is suggested that the solubility of the polymer can be improved by making the diamine compound in the polymerization of polyamic acid-polyimide the structure of the present invention.

Industrial applicability

The diamine of the present invention and the polymer obtained therefrom can be easily provided with various properties by using inexpensive raw materials, and therefore, the diamine can be expected to be useful in the fields of paints, electronic materials, and the like, for example, as a liquid crystal alignment film.

Claims (2)

1. A diamine compound represented by the following general formula (1),

R¹、R²、R³and R⁴Each independently representing H, CH₃Or CF₃Wherein R is¹、R²、R³And R⁴Of which one must represent CH₃Or CF₃，

W₁Represents a single bond or phenylene group, the phenylene group is optionally substituted by a substituent selected from group 1 consisting of a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group, a linear or branched ester group having 1 to 10 carbon atoms, a linear or branched acyl group having 1 to 10 carbon atoms, a carboxyl group, an aldehyde group, a nitro group, and an amino group protected by Boc, and 2W₁Optionally the same or different from each other, wherein each alkyl group in the dialkylamino group is independently a linear or branched alkyl group having 1 to 10 carbon atoms,

W₂represents phenylene optionally substituted with a substituent selected from said group 1, 2W₂Optionally the same or different from each other,

l represents a linear or branched alkylene group having 1 to 10 carbon atoms which is optionally substituted with a substituent selected from the group 1, and-CH in L₂-is optionally selected from-CH ═ CH-, -C ≡ C-, -CF₂-、-C(CF₃)₂-、-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-N(CH₃)-、-NHCONH-、-N(Boc)CONH-、-NHCON(Boc)-、-N(Boc)CON(Boc)-、-NHCOO-、-OCONH-、-CO-、-S-、-SO₂-、-N(Boc)-、-Si(CH₃)₂OSi(CH₃)₂-、-Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂-, a piperidine ring and a piperazine ring, wherein the groups selected from group 2 are optionally adjacent to each other under the condition that the same atoms other than carbon atoms are not bonded to each other.

2. A polymer obtained from the diamine compound represented by the formula (1) according to claim 1.