CN111263761B - 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, R ¹ 、R ² 、R ³ And R ⁴ Each independently represents H and CH ₃ Or CF ₃ Wherein R is ¹ 、R ² 、R ³ And R ⁴ Of which one must represent CH ₃ Or CF ₃ ，W ₁ Represents a single bond or phenylene group, W ₂ Represents a phenylene group, L represents a linear or branched alkylene group having 1 to 10 carbon atoms, CH of the alkylene group ₂ Optionally substituted by oxygen atom or the like. The present invention can provide a diamine which can easily impart various properties by using a highly available raw material, and further can provide a novel polymer obtained therefrom.

Description

Novel Polymers and Diamine Compounds

technical field

This invention relates to the polymer obtained using the novel diamine compound (it may abbreviate also "diamine" in this invention) useful as a raw material of the polymer used for a liquid crystal aligning film, and this diamine. In more detail, the present invention relates to, for example, a polyimide suitable as an electronic material and a diamine compound as a raw material monomer thereof.

Background technique

In general, polyimide resins are used as electronic materials such as liquid crystal display elements, protective materials in semiconductors, insulating materials, and color filters due to their characteristic high mechanical strength, heat resistance, insulation, and solvent resistance. being widely used. In addition, recently, applications as materials for optical communication such as materials for optical waveguides are expected.

In recent years, the development of this field has been remarkable, and accordingly, the materials used are increasingly required to have high characteristics. That is, it is expected not only to be simply excellent in heat resistance and solvent resistance, but also to have various performances suitable for the intended use.

However, polyimides, especially polyimides produced from pyromellitic anhydride (PMDA) and 4,4'-dioxaniline (ODA), which are commonly used as representative examples of wholly aromatic polyimide resins, Amine (Kapton: trade name) cannot be used in the form of a solution due to lack of solubility, and thus can be obtained by heating and dehydrating a precursor called polyamic acid.

Furthermore, among solvent-soluble polyimides (hereinafter soluble polyimides), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone and other amides and lactones with high solubility have been commonly used in the past. Since the organic solvent has a high boiling point, high-temperature firing is unavoidable in order to remove the solvent.

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

On the other hand, in polyamic acid exhibiting high solvent solubility, there is also the problem that sufficient liquid crystal display characteristics cannot be obtained, and volume changes due to imidization are likely to occur. The solvent type is a soluble polyimide.

As a countermeasure against this, the synthesis method of the tetracarboxylic dianhydride using the alicyclic dicarboxylic anhydride which is favorable for solubility in an organic solvent is considered. As an example thereof, it is known to produce various acid dianhydrides by using trimellitic anhydride acid chloride or nuclear hydrogenated trimellitic anhydride acid chloride as a raw material (for example, Patent Document 1).

On the other hand, as for the diamine, similarly to the example of the above-mentioned acid dianhydride, until now, there has been no known method of imparting various properties using an inexpensive raw material.

prior art literature

patent documents

Patent Document 1: Pamphlet WO2006/129771

Contents of the invention

The problem to be solved by the invention

So far, several kinds of diamines having imide rings have been reported, but all of them have low solubility, and therefore, it has been pointed out that the diamine does not dissolve or the molecular weight does not increase.

The object of the present invention is to provide: by using cheap and highly available commercially available raw materials, which can be easily imparted without imidating the polymer of polyamic acid obtained from diamine and acid dianhydride. A method for producing highly soluble diamines with various properties that cannot be obtained, the obtained diamines, and novel polymers obtained therefrom.

solutions to problems

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that a conventional diamine compound having a linear or branched alkylene group and a commercially available compound that is inexpensive and highly available are used as The raw material is a method for producing a polymer that 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 the invention has been completed.

The present invention makes the following gist based on these findings.

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

In formula (1),

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , wherein one of R ¹ , R ² , R ³ and R ⁴ must represent CH ₃ or CF ₃ ,

W ₁ represents a single bond or phenylene, and phenylene is optionally selected from a halogen group, a straight-chain or branched alkyl group with 1 to 10 carbons, a straight-chain or branched alkyl group with 1 to 10 carbons Oxygen, hydroxyl, cyano, dialkylamino (the alkyl groups are each independently a linear or branched alkyl group with 1 to 10 carbons), a linear or branched ester group with 1 to 10 carbons, Substituents in the first group consisting of straight-chain or branched acyl groups, carboxyl groups, aldehyde groups, nitro groups, and Boc-protected amino groups with 1 to 10 carbons, and the two W ₁ are optionally the same or different from each other,

W ₂ represents a phenylene group, the phenylene group is optionally substituted by a substituent selected from Group 1 above, and two W ₂ are optionally the same or different from each other,

L represents a linear or branched alkylene group with 1 to 10 carbons optionally substituted by a substituent selected from Group 1 above, and -CH ₂ - in L is optionally selected from -CH=CH -, -C≡C-, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO ₂ -, -N(Boc)-, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, piperidine substituted by groups in Group 2 consisting of rings and piperazine rings, wherein the groups selected from Group 2 are optionally adjacent to each other on the condition that the same atoms other than carbon atoms are not bonded.

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

The effect of the invention

By using the liquid crystal aligning agent containing the polymer of this invention, the liquid crystal aligning film which voltage retention rate and abrasion resistance are high, and can relax the accumulated electric charge rapidly, and the liquid crystal display element excellent in display characteristic can be provided.

Detailed ways

As mentioned above, this invention is related with the polymer obtained from the diamine compound (it may be referred to as specific diamine below) represented by formula (1) and this diamine compound.

Moreover, the liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer (henceforth a specific polymer) obtained from the diamine which has the structure represented by said formula (1).

Each condition will be described in detail below.

＜Specific diamines＞

As mentioned above, the diamine compound of this invention is represented by formula (1). Here, each substituent of formula (1) is as defined below.

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , wherein one of R ¹ , R ² , R ³ and R ⁴ must represent CH ₃ or CF ₃ ,

W ₁ represents a single bond or phenylene, and phenylene is optionally selected from a halogen group, a straight-chain or branched alkyl group with 1 to 10 carbons, a straight-chain or branched alkyl group with 1 to 10 carbons Oxygen, hydroxyl, cyano, dialkylamino (the alkyl groups are each independently a linear or branched alkyl group with 1 to 10 carbons), a linear or branched ester group with 1 to 10 carbons, Substituents in the first group consisting of straight-chain or branched acyl groups, carboxyl groups, aldehyde groups, nitro groups, and Boc-protected amino groups with 1 to 10 carbons, and the two W ₁ are optionally the same or different from each other,

W ₂ represents a phenylene group, the phenylene group is optionally substituted by a substituent selected from Group 1 above, and two W ₂ are optionally the same or different from each other,

L represents a linear or branched alkylene group with 1 to 10 carbons optionally substituted by a substituent selected from Group 1 above, and -CH ₂ - in L is optionally selected from -CH=CH -, -C≡C-, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO ₂ -, -N(Boc)-, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, piperidine substituted by groups in Group 2 consisting of rings and piperazine rings, wherein the groups selected from Group 2 are optionally adjacent to each other on the condition that the same atoms other than carbon atoms are not bonded to each other.

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , wherein one of R ¹ , R ² , R ³ and R ⁴ must represent CH ₃ or CF ₃ .

Among them, from the aspect of high solubility, it is preferable that R ¹ and R ⁴ represent CH ₃ or CF ₃ , R ² and R ³ represent a hydrogen atom, more preferably R ¹ and R ⁴ represent a methyl group, R ² and R ³ represents a hydrogen atom.

As W ₁ , a single bond or 1,4-phenylene is preferable.

As W ₂ , 1,4-phenylene is preferred.

The alkylene group having 1 to 10 carbon atoms as L may be a straight chain or a branched chain, and examples thereof include straight chains represented by -(CH ₂ ) _n - (where n is 1 to 10). Alkylene, 1-methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane- 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-methylbutane Nylpentane-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 Alkane-1,5-diyl, 3-propylpentane-1,5-diyl, 1-methylhexane-1,6-diyl, 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, 1-phenylpropane-1,3- Branched chain alkylene such as diradical.

These linear or branched alkylene groups (-CH ₂ -) are optionally selected from -CH═CH-, -C≡C-, -CF ₂ -, -C(CF ₃ ) ₂ -, -O- , -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N (Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO ₂ -, -N(Boc)-, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ -, piperidine ring, and piperazine ring are substituted by groups in Group 2.

However, at this time, the groups selected from Group 2 are optionally adjacent to each other on the condition that the same atoms other than carbon atoms are not bonded. In other words, when there are multiple groups selected from Group 2 that can substitute for an alkylene group, the same atoms other than carbon atoms may be used at the bonding portion between the groups selected from Group 2 In the case of bonding, the groups selected from Group 2 cannot be adjacent to each other. As long as the bonding portion between the groups selected from the second group is bonded between carbon atoms or atoms different from each other, the groups selected from the second group can be bonded to each other. Preferably, if the bonding portion between the groups selected from the second group is between carbon atoms, the groups selected from the second group can be bonded to each other.

According to another aspect of the present invention, the groups selected from the second group are not adjacent to each other.

Preferable structures of W ¹ -LW ² include the following structures, but are not limited thereto.

＜Production method of specific diamine＞

Hereinafter, the method of obtaining the said diamine is demonstrated.

The method for synthesizing the specific diamine of the present invention is not particularly limited, for example, the method of reacting a bismaleimide compound represented by the following formula (A) with a compound represented by the following formula (B) , After obtaining the compound represented by the following formula (C), it is imidized to obtain the compound represented by the following formula (D), which is then converted into the compound represented by the formula (1).

In the formula, R ¹ , R ² , R ³ , R ⁴ , W ₁ , W ₂ and L represent the aforementioned meanings, and Q represents NO ₂ or a protected amino group (NHPro).

As the amino protecting group (Pro), acetyl, trifluoroacetyl, pivaloyl, tert-butoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, 2,2,2-trichloroethoxy ylcarbonyl, benzyloxycarbonyl, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, tert-butyldimethylsilyl, tert-butyldiethylsilyl , 9-fluorenylmethyloxycarbonyl, phthaloyl, allyloxycarbonyl, p-toluenesulfonyl, o-nitrobenzenesulfonyl, etc., but are not limited to these.

The amount of the compound represented by the formula (B) is preferably 2 to 4 moles, 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 formula (B) into excess, reaction can be made to progress smoothly, and a by-product can be suppressed.

This reaction is preferably carried out in a solvent.

The solvent can 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 ₂ O, i-Pr ₂ O, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), Dioxane and other ethers; Pentane, hexane, heptane, petroleum ether and other aliphatic hydrocarbons; Benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, Aromatic hydrocarbons such as hydronaphthalene; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate ; Acetonitrile, propionitrile, butyronitrile and other nitriles; etc.

These solvents can be appropriately selected in consideration of the easiness of causing a reaction, etc., and can be used alone or in combination of two or more. If necessary, the solvent may be dried using an appropriate dehydrating agent or desiccant, and used as a non-aqueous solvent.

The usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1-100 mass times with respect to a bismaleimide compound. Preferably, it is 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.

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

This reaction can be performed in the presence of an inorganic base or an organic base as needed.

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

Although it does not specifically limit as the usage-amount of a base, It is 0.1-100 mass times with respect to a bismaleimide compound. Preferably, it is 0 to 30 times by mass, and more preferably 0 to 10 times by mass.

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

When performing imidation, the chemical imidation which adds a catalyst to the solution of the compound represented by the formula (C) obtained by reaction of an amine component and a bismaleimide compound is simple. Chemical imidization is carried out at relatively low temperature for imidization reaction, and it is not easy to cause the decomposition of Pro group in the process of imidization, so it is preferred.

The chemical imidation can be performed by stirring the compound to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. The organic solvents used in this reaction are preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. in terms of solubility, and they can be used alone or in combination of two or more. use.

The concentration of the compound is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint of less likely to cause precipitation of the compound.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among these, pyridine is preferable because it has moderate basicity for advancing the reaction. In addition, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after the reaction becomes easy.

The temperature at the time of imidation reaction is -20-140 degreeC, Preferably it is 0-100 degreeC, and reaction time can be performed for 1-100 hours. The amount of the basic catalyst is 0.5-30 times moles of the amic acid group, preferably 2-20 times the moles, and the amount of the acid anhydride is 1-50 times the moles of the amic acid groups, preferably 3-30 times the moles.

The conditions for producing the specific diamine represented by the formula (1) by reducing the compound represented by the formula (D) when Q is NO ₂ will be described below.

The catalyst used for the reduction reaction is preferably a commercially available activated carbon-supported metal, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. In addition, metal catalysts such as palladium hydroxide, platinum oxide, and Raney nickel may not necessarily be supported on activated carbon. Generally, widely used palladium-activated carbon can obtain good results, so it is preferred.

These reactions are carried out under a hydrogen atmosphere, under normal pressure, or under increased pressure. In addition, metals such as iron, tin, and zinc, or metal salts thereof may be used together with a proton source to reduce nitro groups. A metal and a metal salt can be used individually or in mixture of 2 or more types.

As the proton source, acids such as hydrochloric acid, ammonium salts such as ammonium chloride, and protic solvents such as methanol and ethanol can be used.

In order to advance the reduction reaction more efficiently, the reaction may be carried out in the coexistence of activated carbon. At this time, the amount of 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 advance the reduction reaction more efficiently, the reaction may be carried out under pressure. In the above case, in order to avoid the reduction of the benzene nuclei, it is carried out within the pressurized range up to 20 atmospheres. The reaction is preferably carried out in a range up to 10 atmospheres.

The solvent can 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; ethers such as Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, and dioxane; pentane, hexane, etc. , heptane, petroleum ether and other aliphatic hydrocarbons; benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene and other aromatic hydrocarbons; chloroform, dichloromethane, tetrahydronaphthalene, etc. Halogen-based hydrocarbons such as chlorinated carbon and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; nitriles such as acetonitrile, propionitrile, and butyronitrile; methanol, ethanol Other alcohols; etc. These solvents can be appropriately selected in consideration of the easiness of causing a reaction, etc., and can be used alone or in combination of two or more. If necessary, the solvent may be dried with an appropriate dehydrating agent or desiccant, and used as a non-aqueous solvent.

The usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1-100 mass times with respect to a dinitro compound. Preferably, it is 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited, but is in the range of -100°C to the boiling point of the solvent used, preferably -50 to 150°C. 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) are described below.

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

As for the solvent, any solvent can be used as long as it does not interfere with hydrolysis, such as DMF, DMSO, DMAc, NMP and other aprotic polar organic solvents, Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxygen, etc. Heterocyclohexane and other ethers, pentane, hexane, heptane, petroleum ether and other aliphatic hydrocarbons, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene Aromatic hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane and other halogenated hydrocarbons, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile , propionitrile, butyronitrile and other lower fatty acid esters, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and other alcohols, or water. These solvents can be appropriately selected in consideration of the easiness of causing the reaction, etc. , In the above case, the above-mentioned solvent can be used alone or in combination of two or more. In addition, considering the use of Lewis acid, etc., it can also be used as a non-aqueous solvent using an appropriate dehydrating agent and desiccant.

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

[Preparation method of formula (B)]

Among the compounds represented by the formula (B), the compound (B1) in which Q is NHPro can be prepared by reacting a diamine represented by the following formula (B1-1) with an acid chloride or an acid anhydride of an amine protecting group (Pro). get. In this case, as the diamine (B1-1), a symmetrical diamine is preferable from the viewpoint of suppressing complication of the reaction. In the formula, W ₁ , W ₂ , L, and Pro represent the aforementioned meanings.

Examples of (Pro)-Cl include methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, tert-butyl chloroformate, Benzyl chloroformate, 9-fluorenyl chloroformate, acetyl chloride, trifluoroacetyl chloride, pivaloyl chloride, tert-butoxycarbonyl chloride, ethoxycarbonyl chloride, isopropoxycarbonyl chloride, 2,2,2 -Trichloroethoxycarbonyl chloride, benzyloxycarbonyl chloride, trimethylchlorosilane, triethylchlorosilane, dimethylphenylchlorosilane, tert-butyldimethylsilyl chloride, tert-butyldiethyl Chlorosilane, 9-fluorenylmethyloxycarbonyl chloride, phthaloyl chloride, allyloxycarbonyl chloride, p-toluenesulfonyl chloride, o-nitrobenzenesulfonyl chloride, etc., but not limited to these.

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

The reaction to obtain the compound represented by the above formula (B1) is preferably performed in the presence of a base. As the base, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; trimethylamine, triethylamine, Tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, collidine and other amines; sodium hydride, potassium hydride, sodium tert-butoxide, potassium tert-butoxide, etc. In the case of using a base, amines are preferably used in consideration of the workability of post-treatment of the reaction.

As the reaction solvent, any solvent can be used as long as it is stable under the reaction conditions, is inactive, and does not interfere with the intended reaction. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, and N-methylpyrrolidone can be used; diethyl ether, isopropyl ether, THF, TBME, CPME, dioxa Cyclohexane and other ethers; Pentane, hexane, heptane, petroleum ether and other aliphatic hydrocarbons; Benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin and other aromatics Hydrocarbons; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; acetonitrile, propionitrile, butyronitrile Nitrile etc. Nitrile etc.

These solvents can be appropriately selected in consideration of the easiness of causing a reaction, etc., and can be used alone or in combination of two or more. The above-mentioned solvents can also be used as non-aqueous solvents using appropriate dehydrating agents and desiccants.

The reaction temperature can preferably be selected from a temperature range from -100°C or higher to the boiling point of the reaction solvent used, more preferably -50 to 150°C, particularly preferably 0 to 60°C. 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 above reaction formula (1) can be purified by distillation, recrystallization, column chromatography on silica gel, etc., or can be directly used in the next step without purification.

Among the compounds represented by the formula (B), the compound (B2) in which Q is NO ₂ can be obtained by deprotecting the compound represented by the following formula (B2-1). As conditions for deprotection, the aforementioned methods can be used. In the formula, W ₁ , W ₂ , L, and Pro represent the aforementioned meanings.

In addition, the compound represented by the formula (B2-1) can be represented by halogenation and sulfonylation {methylsulfonyl (OMs), ethanesulfonyl (OEs), p-toluenesulfonyl) represented by the following formula (B2-3) (OTs), trifluoromethanesulfonyl (OTf), etc.} compounds are obtained by reacting nitrolated phenol represented by the following formula (B2-4). In the formula, W ₁ and W ₂ represent the above meanings, and L ¹ represents an alkylene group obtained by removing one CH ₂ (strictly speaking, CH ₂ substituted with an oxygen atom) from the above L.

The compound represented by the formula (B2-3) and the nitrolated phenol represented by the formula (B2-4) used as starting materials in the reaction of this step can be obtained as commercial products, or can be obtained by a known method And manufacture.

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

The reaction is preferably carried out in the presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal carbonates such as 1 to 4 equivalents relative to the compound represented by the formula (B2-3), Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, potassium phosphate, organic bases such as 1,8-diazabicyclo[5,4,0]-7-undecene, etc.

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

As the reaction solvent, dimethylformamide (DMF), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), N - methylpyrrolidone, particularly preferably N-methylpyrrolidone.

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

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

This reaction is preferably carried out in a solvent. Preferred solvents and reaction conditions are the same as those for the production of the above-mentioned compound (1).

The target product in each stage obtained by each of the above reactions may be purified by distillation, recrystallization, or chromatography on a silica gel column, or the reaction liquid may be directly used in the next stage without purification.

＜Polymer＞

The polymer of the present invention is a polymer obtained using the above-mentioned diamine. Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, and the like.

＜Diisocyanate component＞

As a diisocyanate component which provides a polyamide by reaction with the diamine represented by said general formula (1), aromatic diisocyanate, aliphatic diisocyanate, etc. are mentioned, for example. Preferred diisocyanate components are aromatic diisocyanate and aliphatic diisocyanate.

Here, the aromatic diisocyanate means that the group Y of the diisocyanate structure (O=C=N-Y-N=C=O) has a structure including an aromatic ring. Furthermore, aliphatic diisocyanate means that the group Y of the aforementioned isocyanate structure consists of a cyclic or acyclic aliphatic structure.

Specific examples of aromatic diisocyanates include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate (such as 2,4-toluene diisocyanate), 1,4-diisocyanate Isocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanate Diphenylmethane, 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, 2,2' - Benzophenone diisocyanate and the like. Examples of the aromatic diisocyanate preferably include m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene 2,4-diisocyanate.

Specific examples of aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, and the like. As an aliphatic diisocyanate, Isophorone diisocyanate is mentioned preferably. Among them, isophorone diisocyanate and toluene 2,4-diisocyanate are preferable from the viewpoint of polymerization reactivity, and isophorone diisocyanate is more preferable from the viewpoint of availability and polymerization reactivity. isocyanate.

＜Tetracarboxylic dianhydride＞

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

X1 is _a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. _In addition, X1 in the polyimide precursor can be determined according to the solubility of the polymer in the solvent, the coating property when used as a liquid crystal aligning agent, the orientation of the liquid crystal when forming a liquid crystal aligning film, the voltage retention rate, the charge It can be appropriately selected according to the degree of desired characteristics such as accumulation, and may be present in the same polymer as one type, or as a mixture of two or more types.

If specific examples of X1 are insisted on, the structures of the formulas (X- ₁ ) to (X-46) described in Items 13 to 14 of International Publication No. 2015/119168, etc. may be mentioned.

Hereinafter, preferred structures _of X1 are shown, but the present invention is not limited thereto.

＜Dicarboxylic acid＞

Specific examples of the monomer compound used to construct the dicarboxylic acid component of the polyamide by reacting with the diamine represented by the above general formula (1) include terephthalic acid, isophthalic acid, 2-methyl-isophthalic acid, 4-methyl-isophthalic acid, 5-methyl-isophthalic acid, 5-allyloxyisophthalic acid, 5-allyloxycarbonylisophthalic acid Dicarboxylic acid, 5-propargyloxyisophthalic acid, 5-acetoxyisophthalic acid, 5-benzoylamide isophthalic acid, tetrafluoroisophthalic acid, methyl terephthalic acid, tetrafluoroisophthalic acid, Fluoroterephthalic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 1,6-anthracene dicarboxylic acid, 4,4'-dicarboxydicarboxylic acid Benzene, 3,4'-dicarboxybiphenyl, 2,3'-dicarboxybiphenyl, 2,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 3,4'-dicarboxy Diphenyl ether, 2,3'-dicarboxydiphenyl ether, 2,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenyl ether, 3,3'-dimethyl-4,4' -dicarboxybiphenyl, 4,4'-dimethyl-3,3'-dicarboxybiphenyl, 2,2'-dimethyl-4,4'-dicarboxybiphenyl, 3,3'-dicarboxybiphenyl Methoxy-4,4'-dicarboxybiphenyl, 4,4'-dimethoxy-3,3'-dicarboxybiphenyl, 2,2'-dimethoxy-4,4'-di Carboxybiphenyl, 4,4'-dicarboxybenzophenone, 3,4'-dicarboxybenzophenone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxydiphenyl Methane, 3,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylamide, 3,4-dicarboxydiphenylamide, 4 ,4'-dicarboxydiphenylsulfone, 3,4'-dicarboxydiphenylsulfone, 3,3'-dicarboxydiphenylsulfone, 2,2'-dicarboxydiphenylpropane, 1,4 -Bis(4-carboxyphenoxy)benzene, 1,3-bis(4-carboxyphenoxy)benzene, N-[3{(4-carboxyphenyl)carbonylamino}phenyl](4-carboxyphenyl base) formamide, N-[4{(4-carboxyphenyl)carbonylamino}phenyl](4-carboxyphenyl)formamide, 4,4'-(4-carboxyphenoxyphenyl)methane, 4,4'-bis(4-carboxyphenoxy)diphenylsulfone, 2,2'-bis[4-(4-carboxyphenoxy)phenyl]propane, 2,2-bis(4-carboxy phenyl)hexafluoropropane, 2,2'-bis[4-(4-carboxyphenoxy)phenyl]hexafluoropropane, 1,5-bis(4-carboxyphenyl)pentane, 1,4- Bis(4-carboxyphenyl)butane, 1,3-bis(4-carboxyphenyl)propane, 4,4'-bis(carboxyphenyl)pentane-1,5-dioate, 4,4 Aromatic or aromatic-containing dicarboxylic acids such as '-bis(carboxyphenyl)hexane-1,6-dioate and 4,4'-bis(carboxyphenyl)heptane-1,7-dioate And their acid halides and alkyl esters.

Furthermore, 1,3-dicarboxycyclohexane, 1,4-dicarboxycyclohexane, 1,2-dicarboxycyclobutane, 1,3-dicarboxycyclobutane, bis(4-carboxycyclobutane, Alicyclic dicarboxylic acids such as cyclohexyl)methane, bis(4-carboxy-3-methylcyclohexyl)methane, bis(4-carboxycyclohexyl)ether, bis(4-carboxy-3-methylcyclohexyl)ether Acids and their acid halides and alkyl esters, and a mixture of two or more of them can also be used.

When obtaining the polymer of this invention by the polymerization reaction with the diamine component containing the diamine compound represented by said formula (1), a well-known synthesis method can be used. Usually, it is a method of making at least 1 sort(s) chosen from the diisocyanate component, the dicarboxylic acid component, and the tetracarboxylic acid component, and a diamine component react in an organic solvent. The reaction of at least one selected from the diisocyanate component, the dicarboxylic acid component, and the tetracarboxylic acid component with the diamine component is relatively easy in an organic solvent, and it is advantageous in that no by-product is produced.

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

Examples of organic solvents usable here include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl Ketone, methyl nonyl 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, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate , propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, 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 acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy Methyl ethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3-methoxypropionate butyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N -Dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. These may be used individually or in mixture.

Moreover, since the moisture in an organic solvent will hinder a polymerization reaction, it is preferable to use what was dehydrated and dried as much as possible as an organic solvent.

When reacting at least one selected from diisocyanate components, dicarboxylic acid components, and tetracarboxylic acid components with diamine components in an organic solvent, the following method can be mentioned: the diamine component is dispersed or dissolved in the organic solvent The solution is stirred, and at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component is added directly, or dispersed or dissolved in an organic solvent and added; on the contrary, dispersed in an organic solvent or A method of adding a diamine component to a solution in which at least one selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component is dissolved; alternately adding a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component At least one method with a diamine component in the body; etc., any of these methods can be used. In addition, when at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component or the diamine component contains a plurality of compounds, the reaction may be carried out in a pre-mixed state, or may be sequentially mixed separately. In the reaction, the separately reacted low-molecular-weight bodies can be mixed and reacted to obtain high-molecular-weight bodies.

The polymerization temperature at this time can be any temperature from -20°C to 150°C, preferably in the range from -5°C to 100°C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it will be difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution will become excessively high, and uniform stirring will become difficult. Therefore, selected from The total concentration in the reaction solution of at least one of a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component, and a diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. Initially, the reaction may be carried out at a high concentration, and the organic solvent may be added thereafter.

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 diisocyanate components, dicarboxylic acid components and tetracarboxylic acid components to the total number of moles of diamine components is preferably from 0.8 to 1.2. As in a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polymer to be produced.

When recovering the produced polymer from the reaction solution of the polymer of the present invention, the reaction solution may be thrown into a poor solvent and precipitated. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer thrown in and precipitated in a poor solvent can be recovered by filtration, and then dried at normal temperature or heated under normal pressure or reduced pressure. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the reprecipitation recovery is carried out, and this operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of poor solvents in this case include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more poor solvents selected from them because the efficiency of purification will further increase.

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

(In formula [1], A ₁ is a divalent organic group, A ₂ is a divalent group shown in the following formula (A2),

In formula (A2), R ¹ , R ² , R ³ , R ⁴ , W ₁ , W ₂ and L represent the aforementioned meanings, and C ₁ and C ₂ are hydrogen atoms or alkyl groups with 1 to 3 carbons, and optionally same or different. )

In the above formula [1], A ₁ and A ₂ may be one kind of polymer having the same repeating unit, and A ₁ and A ₂ may be multiple types of repeating units having different structures. things.

In the above formula [1], A ₁ is a group derived from a diisocyanate component as a raw material. In addition, A ₂ is a group derived from a diamine component as a raw material.

According to a preferred aspect of the present invention, A ₁ is preferably a group 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].

In formula [2], A ₃ is each independently a tetravalent organic group, and A ₂ is a divalent group represented by the above formula (A2). R ₁₁ is a hydrogen atom or an alkyl group with 1 to 5 carbons, and C ₁ to C ₂ are each independently a hydrogen atom, or an alkyl group with 1 to 10 carbons optionally having a substituent, or an alkene with 2 to 10 carbons. group or an alkynyl group with 2 to 10 carbon atoms.

Specific examples of the above-mentioned alkyl group in R ₁₁ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and the like. R ₁₁ is preferably a hydrogen atom or a methyl group from the viewpoint of easiness of imidation by heating.

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

In formula [3], A ₄ is each independently a divalent organic group derived from a dicarboxylic acid, and A ₂ , C ₁ and C ₂ are as above.

It should be noted that when producing the polymer of the present invention, two or three of the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component can be reacted simultaneously or sequentially, for example, the diisocyanate component When reacting with a tetracarboxylic-acid component, the polyurea polyamic acid which is a polymer which has the repeating unit represented by said formula [1] and the repeating unit represented by said formula [2] can be obtained.

＜Manufacturing method of polyamic acid＞

The polyamic acid which is a polyimide precursor used by this invention can be synthesize|combined by the method shown below.

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

From the solubility of monomers and polymers, the organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc., and one of them can be used Or use it in mixture of 2 or more types.

The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained.

The polyamic acid obtained above can be poured into a poor solvent, fully stirring the reaction solution, and a polymer can be precipitated and recovered. Moreover, after performing precipitation several times and washing|cleaning with a poor solvent, it can dry at normal temperature or heat-dry, and the 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, toluene, and the like, preferably water, methanol, ethanol, 2-propanol, and the like.

＜Manufacturing method of polyimide＞

The polyimide used by this invention can be manufactured by imidating the said polyamic acid.

When producing a polyimide from a polyamic acid, the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and a tetracarboxylic dianhydride is simple. The chemical imidization is carried out at a relatively low temperature, and the molecular weight of the polymer is less likely to decrease during the imidization process, so it is preferred.

The chemical imidation can be performed by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among these, pyridine is preferable because it has moderate basicity for advancing the reaction. Moreover, as an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride etc. are mentioned, Among them, since purification after completion|finish of reaction becomes easy when acetic anhydride is used, it is preferable.

The temperature at the time of imidation reaction is -20-140 degreeC, Preferably it is 0-100 degreeC, and reaction time can be performed for 1-100 hours. The amount of the basic catalyst is 0.5-30 times the mole of the polyamic acid group, preferably 2-20 times the mole, and the amount of the acid anhydride is 1-50 times the mole of the polyamic acid group, preferably 3-30 times the mole. The imidization rate of the obtained polymer is controlled by adjusting the catalyst amount, temperature, and reaction time.

In the solution after the imidation reaction of polyamic acid, the added catalyst etc. remains, therefore, preferably by the means described below, reclaim the imidation polymer that obtains, carry out redissolving with organic solvent, form the present invention Liquid crystal alignment agent.

A polymer can be deposited by pouring into a poor solvent, stirring well about the solution of the polyimide obtained above. The precipitation is carried out several times, and after washing with a poor solvent, drying at room temperature or heating can be performed to obtain a purified polymer powder.

The aforementioned poor solvent is not particularly limited, but methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc., preferably methanol, ethanol, 2-propanol, acetone, etc.

＜Manufacture of polyimide precursor-polyamic acid ester＞

The polyamic acid ester which is a polyimide precursor used by this invention can be manufactured by the manufacturing method of (i), (ii) or (iii) shown below.

(i) When it is produced from polyamic acid

Polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, the polyamic acid and the esterifying agent are reacted for 30 minutes to 24 hours, preferably 1 to 4 hours, at -20°C to 150°C, preferably 0°C to 50°C, in the presence of an organic solvent, so that manufacture.

As the esterification agent, those that can be easily removed by purification are preferred, such as N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N -Dimethylformamide dipropyl acetal, N,N-dimethylformamide dipentyl butyl acetal, N,N-dimethylformamide di-tert-butyl acetal, 1-methyl -3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6-dimethoxy- 1,3,5-triazin-2-yl)-4-methylmorpholine hydrochloride, etc. It is preferable that the addition amount of an esterification agent is 2-6 molar equivalent with respect to 1 mol of repeating units of a polyamic acid.

As an organic solvent, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylethyl amide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxyl-4-methyl-2-pentanone, or the following formula [D- 1] to the solvent represented by the formula [D-3].

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group with 1 to 3 carbon atoms, in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, it can mix and use with the said solvent in the range which does not precipitate the polyimide precursor produced|generated. Moreover, since the moisture in a solvent interferes with a polymerization reaction and further becomes a cause of hydrolysis of the polyimide precursor produced|generated, it is preferable to use what was dehydrated and dried as a solvent.

From the viewpoint of polymer solubility, the solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone, and they can be used alone or in combination. Use the above. The concentration at the time of production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained.

(ii) When it is produced by reaction of tetracarboxylic acid diester dichloride and diamine

Polyamic acid ester can be manufactured from tetracarboxylic acid diester dichloride and diamine.

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

As the above-mentioned base, pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used, and pyridine is preferred because the reaction proceeds mildly. As for the addition amount of a base, it is preferable that it is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride from the point which is the quantity which removes easily and obtains a high molecular weight body easily.

From the viewpoint of the solubility of monomers and polymers, the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone, and these can be used alone or in combination of two or more. The polymer concentration at the time of production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained. Moreover, in order to prevent the hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable to dehydrate the solvent used for manufacture of polyamic acid ester as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(iii) Manufactured from tetracarboxylic acid diester and diamine

Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine.

Specifically, tetracarboxylic acid diester and diamine are carried out at 0°C to 150°C, preferably 0°C to 100°C, for 30 minutes to 24 hours, preferably 3 to 15 hours, in the presence of a condensing agent, a base and an organic solvent. Hours of reaction, which can be manufactured.

The aforementioned condensing agents can be used: triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N,N' -Carbonyldiimidazole, Dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyl Urea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2- Thio-3-benzoxazolyl) diphenyl phosphonate, etc. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to a tetracarboxylic-acid diester.

As the aforementioned base, tertiary amines such as pyridine and triethylamine can be used. It is preferable that the addition amount of a base is 2-4 times mole with respect to a diamine component from the point which is the quantity which is easy to remove, and obtains a high molecular weight body easily.

In addition, in the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. It is preferable that the addition amount of a Lewis' acid is 0-1.0 times mole with respect to a diamine component.

Since the polyamic acid ester of high molecular weight can be obtained among the manufacturing methods of the said 3 kinds of polyamic acid esters, the manufacturing method of said (i) or said (ii) is especially preferable.

A polymer can be deposited by pouring into a poor solvent, stirring well about the solution of the polyamic acid ester obtained above. Precipitation may be performed several times, and after washing|cleaning with a poor solvent, dry at normal temperature or heat-dry, and obtain the powder of the polyamic acid ester purified. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

When producing the polymer of the present invention, in the above production method, diamine represented by the formula (1) can be used as the diamine. In addition, at this time, as the diamine, a substance other than the substance represented by the formula (1) can be used. If it is necessary to show specific examples, the following diamines can be mentioned: the diamine having two amino groups bonded to the structure of the formula (2) described in International Publication No. 2015/119168, item 4, and, item 8 Diamines having two amino groups bonded to the structures of formulas (Y-1) to (Y-97) and formulas (Y-101) to (Y-118) described in Item 12; International Publication No. 2013/008906 The diamine of formula (2) recorded in item 6 of International Publication 2015/122413; the diamine of formula (1) recorded in item 8 of International Publication 2015/122413; the formula (3) recorded in item 8 of International Publication 2015/060360 A diamine having two amino groups bonded to its structure; a diamine of formula (1) described in Item 8 of Japanese Laid-Open Patent Publication 2012-173514; a formula (A) described in Item 9 of International Publication Publication 2010-050523 ~ Diamines of (F); etc.

The polymer of the present invention obtained in this way can be used not only as a paint, but also for applications such as insulating films, film substrates, liquid crystal aligning films, and protective films.

Example

Examples are given below to describe the present invention in more detail, but the present invention is not limited thereto.

The structures of diamine compounds used in Examples are shown below.

＜Diamine compound＞

DA-1 to DA-8 and DA-10 to DA-15 are novel compounds not disclosed in literature etc., and their synthesis methods will be described in detail in Synthesis Examples 1 to 14 below.

DA-9 was synthesized using the synthesis method described in the patent document (WO2017-057854).

Abbreviations of 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: ethanol.

IPA: Isopropyl Alcohol.

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

＜Measurement of ¹ HNMR＞

Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) "INOVA-400" (manufactured by Varian) 400 MHz.

Solvent: deuterated chloroform (CDCl ₃ ) or deuterated N,N-dimethylsulfoxide ([D ₆ ]-DMSO).

Standard substance: tetramethylsilane (TMS).

(Synthesis Example 1)

Synthesis of [DA-1]:

Put 4-[(4-aminophenoxy)methoxy]aniline (230.0g, 999mmol) and THF (1600g) into a 3L four-necked flask, add di-tert-butyl dicarbonate (218.0g, 999 mmol), stirred at room temperature. After completion of the reaction, the reaction liquid was concentrated, and the obtained residue was separated by silica gel column chromatography (ethyl acetate:hexane=1:1 volume ratio) to obtain 158.0 g of [DA-1-1].

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

Put [DA-1-2] (169.8g, 200mmol) and CH ₂ Cl ₂ (2500g) into a 3L four-neck flask, drop trifluoroacetic acid (204.1g, 1000mmol) in a water bath, and stir at room temperature . After completion of the reaction, the reaction liquid was concentrated, pure water (3 L) was added to the obtained crude product, and triethylamine was used for neutralization. The precipitate was filtered, and THF (500 g) and MeOH (700 g) were added to the obtained crude product, and 106.0 g of [DA-1] (white solid) were obtained by reslurry washing|cleaning at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-1].

¹ H NMR(400MHz,[D ₆ ]-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]:

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

[DA-2-1] (46.4g, 129mmol) and NMP (460g) were put into a 3L four-necked flask, and 1,3-DMCBDA (14.5g, 65mmol) was added to the water bath, and it stirred at room temperature for 6 hours. Next, pyridine (30.7 g, 388 mmol) and acetic anhydride (19.8 g, 194 mmol) were thrown into the reaction liquid, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was filtered off. MeOH (400 ml) was added to the obtained crude product, and 41.1 g of [DA-2-2] was obtained by reslurry washing|cleaning at room temperature.

[DA-2-2] (41.1g, 45mmol) and CH ₂ Cl ₂ (600g) were put into a 3L four-necked flask, and trifluoroacetic acid (46.4g, 454mmol) was added dropwise in a water bath, followed by stirring at room temperature . After completion of the reaction, the reaction liquid was concentrated, and pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, EtOH (100g) was added to the obtained crude product, and 25.3 g of [DA-2] (white solid) were obtained by performing reslurry washing at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-2].

¹ H NMR(400MHz,[D ₆ ]-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]:

Put 4-[6-(4-aminophenoxy)hexyloxy]aniline (90.0g, 300mmol) and THF (600g) into a 3L four-necked flask, add di-tert-butyl dicarbonate (65.4 g, 300mmol), stirred at room temperature. After completion of the reaction, the reaction liquid was concentrated, and the obtained residue was separated by silica gel column chromatography (ethyl acetate:hexane=1:1 volume ratio) to obtain 48.0 g of [DA-3-1].

[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 water bath, and it stirred at room temperature for 6 hours. Next, pyridine (28.4 g, 360 mmol) and acetic anhydride (18.4 g, 180 mmol) were thrown into the reaction liquid, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was filtered off. MeOH (400 ml) was added to the obtained crude product, and 42.5 g of [DA-3-2] were obtained by reslurry washing|cleaning at room temperature.

[DA-3-2] (42.5g, 43mmol) and CH ₂ Cl ₂ (640g) were put into a 3L four-neck flask, and trifluoroacetic acid (43.9g, 430mmol) was added dropwise in a water bath, and then carried out at room temperature. Stir. After completion of the reaction, the reaction liquid was concentrated, and pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, MeOH (100g) was added to the obtained crude product, and 26.3 g of [DA-3] (purple solid) were obtained by reslurry washing|cleaning at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-3].

¹ H NMR(400MHz,[D ₆ ]-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]:

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

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

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

[DA-4-3] (60.8g, 235mmol) and NMP (600g) were put into a 2L four-necked flask, and 1,3-DMCBDA (24.8g, 111mmol) was added to the water bath, and it stirred at room temperature for 6 hours. Next, pyridine (55.8 g, 705 mmol) and acetic anhydride (35.9 g, 352 mmol) were thrown into the reaction liquid, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was filtered off. EtOH (1000g) was added to the obtained crude product, and [DA-4-4]79.1g was obtained by reslurry washing|cleaning at room temperature.

[DA-4-4] (79.0g, 112mmol) and DMF (800g) were put into a 3L four-neck flask, and after nitrogen substitution, 5wt% Pd/C (7.9g) was added to carry out hydrogen substitution, and stirred at room temperature . After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation with a rotary evaporator, ethyl acetate (1500 g) was added, and reslurry washing was performed at room temperature to obtain 69.9 g of [DA-4] (white solid). The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-4].

¹ H NMR(400MHz,[D ₆ ]-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), EtOH (100g) were put into a 1L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (8.0g) was added for hydrogen replacement. Stirring was carried out at room temperature. After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation with a rotary evaporator to obtain 73.9 g of [DA-5-1].

[DA-5-1](73.9g, 225mmol) and NMP (700g) were put into a 2L four-necked flask, and 1,3-DMCBDA (23.7g, 106mmol) was added to the water bath, and it stirred at room temperature for 6 hours. Next, pyridine (53.4 g, 675 mmol) and acetic anhydride (34.5 g, 338 mol) were thrown into the reaction liquid, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was filtered off. EtOH (1000g) was added to the obtained crude product, and 85.4g of [DA-5-2] was obtained by reslurry washing|cleaning at room temperature.

[DA-5-2](85.4g, 101mmol), 6N-hydrochloric acid aqueous solution (200g), and ethyl acetate (800g) were put into a 2L four-necked flask, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (1.2 L), and neutralized with triethylamine. The precipitate was filtered off, ethyl acetate (1,500 g) was added, and 61.1 g of [DA-5] was obtained by performing reslurry washing at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-5].

¹ H NMR(400MHz,[D ₆ ]-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]:

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

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

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

[DA-6-3] (62.6g, 230mmol) and NMP (900g) were put into a 2L four-necked flask, and 1,3-DMCBDA (25.5g, 114mmol) was added to the water bath, and it stirred at room temperature for 6 hours. Next, pyridine (54.5 g, 690 mmol) and acetic anhydride (35.2 g, 345 mmol) were thrown into the reaction liquid, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (4 L), and the precipitate was filtered off. MeOH (500 g) was added to the obtained crude product, and 82.0 g of [DA-6-4] was obtained by reslurry washing|cleaning at room temperature.

[DA-6-4] (80.0g, 109mmol) and DMF (3200g) were put into a 5L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (8.0g) was added to carry out hydrogen replacement, at 60°C Stir. After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation with a rotary evaporator, ethyl acetate (1000 g) was added, and reslurry washing was performed at room temperature to obtain 59.1 g of [DA-6] (magenta solid). The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-6].

¹ H NMR(400MHz,[D ₆ ]-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), EtOH (90g) were put into a 1L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (8.7g) was added for hydrogen replacement. Stirring was carried out at room temperature. After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was subjected to solvent distillation with a rotary evaporator to obtain 65.8 g of [DA-7-1].

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

[DA-7-2](83.0g, 96mmol), 6N-hydrochloric acid aqueous solution (170g), and ethyl acetate (700g) were put into a 2L four-necked flask, and it stirred at 60 degreeC. After completion of the reaction, the reaction system was poured into pure water (1 L), and neutralized with triethylamine. The precipitate was filtered off, ethyl acetate (500 g) was added, and 25.2 g of [DA-7] was obtained by performing reslurry washing at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-7].

¹ H NMR(400MHz,[D ₆ ]-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]:

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

[DA-8-1] (67.2 g, 121 mmol) and acetic acid (400 g) were thrown into a 1 L four-necked flask, and it stirred at 100 degreeC. After completion of the reaction, the reaction system was poured into pure water (1.5 L), and the precipitate was filtered off. MeOH (60 g) was added to the obtained crude product, and 30.4 g of [DA-8-2] were obtained by performing reslurry washing|cleaning at room temperature.

[DA-8-2] (30.4g, 58mmol) and DMF (450g) were put into a 1L four-necked flask, and after nitrogen substitution, 5wt% Pd/C (3.0g) was added to carry out hydrogen substitution, and stirred at room temperature . After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was poured into pure water (3 L), and the precipitate was filtered off. MeOH (80 g) was added to the obtained crude product, and 25.9 g of [DA-8] (white solid) were obtained by reslurry washing|cleaning at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-8].

¹ H NMR(400MHz,[D ₆ ]-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]:

Drop into 2-(4-nitrophenyl) ethylamine hydrochloride (25.0g, 123mmol), triethylamine (14.2g, 140mmol), THF (250g) in 1L four-necked flask, add 1, After 2,3,4-cyclobutanetetracarboxylic dianhydride (11.7 g, 60 mmol), it stirred at room temperature for 6 hours. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was filtered off. IPA (500g) was added to the obtained crude product, and 21.8g of [DA-10-1] was obtained by performing reslurry washing|cleaning at room temperature.

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

[DA-10-2] (19.3g, 39mmol) and DMF (400g) were put into a 1L four-neck flask, and after nitrogen substitution, 5wt% Pd/C (2.0g) was added to carry out hydrogen substitution, and stirred at room temperature . After the reaction, the reaction solution was filtered with a 0.45 μm membrane filter to remove Pd/C. The obtained filtrate was poured into pure water (3 L), and the precipitate was filtered off. MeOH (300 g) was added to the obtained crude product, and 15.2 g of [DA-10] (white solid) were obtained by reslurry washing|cleaning at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-10].

¹ H NMR (400MHz, [D ₆ ]-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]:

Put N,N'-bis[2-(4-aminophenyl)ethyl]urea (134.4g, 450mmol) and DMF (650g) into a 1L four-necked flask, add di-tert-butyl dicarbonate dropwise in a water bath After (32.8 g, 150 mmol), it was stirred at room temperature. After the reaction, the reaction solution was concentrated, pure water (1.5 L) was added, and the precipitate was filtered off. CHCl ₃ (1.5 L) was added to the obtained crude product, and the organic layer was washed with 10 wt % acetic acid aqueous solution (1.5 L). Furthermore, after neutralizing the organic layer with triethylamine and washing|cleaning with pure water (2L), it concentrated and obtained 50.8g of [DA-11-1].

[DA-11-1] (49.0g, 123mmol) and NMP (500g) were put into a 2L four-necked flask, and 1,3-DMCBDA (13.5g, 60mmol) was added to the water bath, and it stirred at room temperature for 6 hours. Next, pyridine (29.4 g, 369 mmol) and acetic anhydride (18.8 g, 185 mol) were thrown into the reaction liquid, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (2.5 L), and the precipitate was filtered off. Next, THF (800g) was added to the obtained crude product, after it was completely dissolved, it was concentrated at 40°C until solids were precipitated, MeOH (200g) was added, and reslurry cleaning was carried out at room temperature to obtain [DA-11-2 ] 47.7 g.

[DA-11-2] (47.7 g, 48 mmol) and CHCl ₃ (480 g) were charged into a 1 L four-necked flask, and trifluoroacetic acid (55.7 g, 484 mmol) was added dropwise in a water bath, followed by stirring at 50°C. After completion of the reaction, the reaction liquid was poured into hexane (500 g), and the precipitate was filtered off. Next, MeOH (500 g) was added to the obtained crude product, it neutralized with triethylamine, and the deposit was filtered off. Next, DMF (300g) was added to the obtained crude product, heated to 60°C to dissolve it completely, concentrated at 40°C until solids were precipitated, THF (600g) was added, and reslurried at room temperature for washing to obtain [DA-11] (white solid) 25.2 g. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-11].

¹ H NMR(400MHz,[D ₆ ]-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]:

Put 1-(4-nitrophenyl)-4-piperidinamine (39.0g, 116mmol) and NMP (400g) into a 500mL four-neck flask, add 1,3-DMCBDA (12.8g, 47mmol) in a water bath Thereafter, stirring was performed at 50° C. for 6 hours. Next, pyridine (27.6 g, 349 mmol) and acetic anhydride (17.8 g, 175 mol) were thrown into the reaction liquid, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was filtered off. Next, MeOH (250 g) was added to the obtained crude product, and reslurry washing was performed at room temperature to obtain 32.1 g of [DA-12-1].

[DA-12-1] (32.1g, 51mmol) and DMF (960g) were put into a 2L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (3.2g) was added to carry out hydrogen replacement at 50°C. Stir. After completion of the reaction, the reaction solution was filtered, 2N-hydrochloric acid aqueous solution (1 L) was added to the obtained filter residue, and the Pd/C was removed by filtering with a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was filtered off. Furthermore, MeOH (100g) was added to the obtained crude product, and 22.1 g of [DA-12] (carmine solid) were obtained by performing reslurry washing|cleaning at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-12].

¹ H NMR(400MHz,[D ₆ ]-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]:

Put 4-amino-1-tert-butoxycarbonylpiperidine (70.0g, 350mmol) and NMP (700g) into a 2L four-necked flask, add 1,3-DMCBDA (38.4g, 171mmol) in a water bath, and then Stir at room temperature for 6 hours. Next, pyridine (82.9 g, 1049 mmol) and acetic anhydride (53.5 g, 524 mol) were thrown into the reaction liquid, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (3.5 L), and the precipitate was filtered off. Next, MeOH (300g) was added to the obtained crude product, and 92.0 g of [DA-13-1] were obtained by performing reslurry washing|cleaning at room temperature.

[DA-13-1] (92.0 g, 170 mmol) and CHCl ₃ (920 g) were put into a 2L four-neck flask, and trifluoroacetic acid (193.3 g, 1700 mol) was added dropwise in a water bath, followed by stirring at 50°C. After completion of the reaction, the precipitate was filtered off, ethyl acetate (300 g) was added to the obtained crude product, and 97.8 g of [DA-13-2] was obtained by performing reslurry washing at room temperature.

[DA-13-2] (40.0g, 65mmol), 2-(4-nitrophenyl) ethyl bromide (32.8g, 143mmol), potassium carbonate (35.9g, 260mmol), NMP (400g) was stirred at 60°C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was filtered off. MeOH (200 g) was added to the obtained crude product, and 27.5 g of [DA-13-3] was obtained by performing reslurry washing|cleaning at 60 degreeC.

[DA-13-3] (29.3g, 43mmol) and DMF (900g) were put into a 3L four-neck flask, and after nitrogen replacement, 5wt% Pd/C (2.9g) was added to carry out hydrogen replacement, at 60°C Stir. After completion of the reaction, the reaction solution was concentrated, 2N-hydrochloric acid aqueous solution (1 L) was added to the obtained crude product, and Pd/C was removed by filtering with a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was filtered off. Furthermore, MeOH (100g) was added to the obtained crude product, and 8.7g of [DA-13] (color solid) was obtained by performing reslurry washing at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-13].

¹ H NMR(400MHz,[D ₆ ]-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]:

Put 4-(4-aminophenyl)piperidine-1-carboxylate tert-butyl ester (22.8g, 82mmol) and NMP (230g) into a 500mL four-necked flask, add 1,3-DMCBDA (8.9g , 40 mmol), stirred at room temperature for 6 hours. Next, pyridine (39.1 g, 494 mmol) and acetic anhydride (25.2 g, 247 mol) were thrown into the reaction liquid, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (1.5 L), and the precipitate was filtered off. Next, MeOH (100g) was added to the obtained crude product, and 28.5 g of [DA-14-1] were obtained by performing reslurry washing|cleaning at room temperature.

[DA-14-1] (28.5 g, 39 mmol) and CHCl ₃ (290 g) were put into a 500 mL four-necked flask, and trifluoroacetic acid (43.9 g, 385 mol) was added dropwise in a water bath, followed by stirring at 50°C. After completion of the reaction, the precipitate was filtered off, MeOH (150 g) was added to the obtained crude product, and 29.2 g of [DA-14-2] was obtained by performing reslurry washing at room temperature.

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

[DA-14-3] (26.1g, 31mmol) and DMF (800g) were put into a 3L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (2.6g) was added to carry out hydrogen replacement, at 80°C Stir. After completion of the reaction, the reaction solution was concentrated, 2N-hydrochloric acid aqueous solution (1 L) was added to the obtained crude product, and Pd/C was removed by filtering with a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was filtered off. Further, MeOH (100 g) was added to the obtained crude product, and 12.3 g of [DA-14] (skin color solid) were obtained by performing reslurry washing at room temperature. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-14].

¹ H NMR(400MHz,[D ₆ ]-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]:

Put tert-butyl 4-(4-aminophenyl)piperazine-1-carboxylate (33.2g, 120mmol) and NMP (330g) into a 1L four-necked flask, add 1,3-DMCBDA (13.1g , 59 mmol), stirred at room temperature for 6 hours. Next, pyridine (28.4 g, 359 mmol) and acetic anhydride (18.3 g, 180 mol) were thrown into the reaction liquid, and it stirred at 50 degreeC. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was filtered off. Next, MeOH (150 g) was added to the obtained crude product, and reslurry washing was performed at room temperature to obtain 40.7 g of [DA-15-1].

[DA-15-1] (40.7 g, 55 mmol) and CHCl ₃ (400 g) were put into a 2L four-necked flask, and trifluoroacetic acid (62.6 g, 548 mol) was added dropwise in a water bath, followed by stirring at 50°C. After completion of the reaction, the precipitate was filtered off, THF (200 g) was added to the obtained crude product, and 21.8 g of [DA-15-2] was obtained by reslurry washing at 50°C.

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

[DA-14-3] (17.9g, 21mmol) and DMF (540g) were put into a 3L four-necked flask, and after nitrogen replacement, 5wt% Pd/C (1.8g) was added to carry out hydrogen replacement, at 80°C Stir. After the reaction, the reaction solution was concentrated, 2N-hydrochloric acid aqueous solution (500 mL) was added to the obtained crude product, and the Pd/C was removed by filtering with a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was filtered off. Furthermore, MeOH (50g) was added to the obtained crude product, and reslurry washing was performed at 60 degreeC, and [DA-15] (color solid) 5.7g was obtained. The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target [DA-15].

¹ H NMR(400MHz,[D ₆ ]-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 saturation solubility in NMP of diamine compound at room temperature>

(Example 1)

The diamine compound [DA-1] was added to NMP (2 g) heated at 60° C. until a dissolved residue was formed, and stirred at 60° C. for 1 hour. After heating, it was naturally cooled at room temperature for 6 hours, and the precipitate was removed to prepare a saturated solution of [DA-1] in NMP 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 (39 g) was added to the prepared saturated solution (1 g), the peak area was measured, and the saturation solubility to NMP at room temperature of [DA-1] was calculated.

(Examples 2-9, Comparative Examples 1-2)

As shown in Table 1, Examples 2-9 were also calculated by the same method as Example 1. In addition, Comparative Examples 1 and 2 were also calculated by the same method.

[Table 1]

As shown in Table 1, it was confirmed that the saturated solubility to NMP of the diamine compounds (DA-1 to DA-8, DA-11) of the present invention of Examples 1 to 9 at room temperature was comparable to that of Comparative Example 1. Shows good solubility compared to amine compound (DA-9). In addition, it was confirmed that the diamine compound (DA-8) of Example 8 exhibited better solubility than the diamine compound (DA-10) of Comparative Example 2 in terms of saturation solubility in NMP at room temperature. From the above, it was suggested that the solubility with respect to NMP can be improved by making a diamine compound into the structure of this invention.

＜Measurement of molecular weight of polymer＞

The molecular weight of the polyimide in the embodiment, polyamic acid, polyamic acid ester uses the normal temperature gel permeation chromatography (GPC) device (GPC-101) of Co., Ltd. Shodex company system, Shodex company system column (KD-803, KD-805) was measured as follows.

Column temperature: 50°C

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

Flow rate: 1.0mL/min

Standard samples for standard curve preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: about 900,000, 150,000, 100,000, and 30,000), and polyethylene glycol manufactured by Polymer Laboratories Ltd. (molecular weight: about 12,000, 4,000, and 1,000) .

(polymerization example 1)

Make the CBDA of 0.18g (0.93mol) and the DA-1 of 0.64g (1.0mmol) in NMP (7.48g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-1 ). The polyamic acid-polyimide had a number average molecular weight of about 29,500.

(polymerization example 2)

Make the CBDA of 0.18g (0.93mol) and the DA-2 of 0.70g (1.0mmol) in NMP (7.98g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-2 ). The polyamic acid-polyimide had a number average molecular weight of about 30,000.

(polymerization example 3)

Make the CBDA of 0.18g (0.93mol) and the DA-3 of 0.78g (1.0mmol) in NMP (8.74g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-3 ). The polyamic acid-polyimide had a number average molecular weight of about 32,000.

(polymerization example 4)

Make the CBDA of 0.18g (0.93mol) and the DA-4 of 0.64g (1.0mmol) in NMP (7.44g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-4 ). The polyamic acid-polyimide had a number average molecular weight of about 14,800.

(polymerization example 5)

0.18g (0.93mol) of CBDA and 0.64g (1.0mmol) of DA-5 were reacted in NMP (7.44g) at room temperature for 16 hours to prepare polyamic acid-polyimide polymerization solution (PI-5) . The polyamic acid-polyimide had a number average molecular weight of about 9900.

(polymerization example 6)

Make the CBDA of 0.18g (0.93mol) and the DA-6 of 0.67g (1.0mmol) in NMP (7.69g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-6 ). The polyamic acid-polyimide had a number average molecular weight of about 8700.

(polymerization example 7)

Make the CBDA of 0.18g (0.93mol) and the DA-7 of 0.67g (1.0mmol) in NMP (7.69g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-7 ). The polyamic acid-polyimide had a number average molecular weight of about 16,900.

(polymerization example 8)

Make the CBDA of 0.18g (0.93mol) and the DA-8 of 0.46g (1.0mmol) in NMP (5.78g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-8 ). The polyamic acid-polyimide had a number average molecular weight of about 8900.

(polymerization example 9)

Make the CBDA of 0.18g (0.93mol) and the DA-9 of 0.40g (1.0mmol) in NMP (5.28g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-9 ). The polyamic acid-polyimide had a number average molecular weight of about 13,600.

(polymerization example 10)

Make the CBDA of 0.18g (0.93mol) and the DA-10 of 0.43g (1.0mmol) in NMP (5.53g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-10 ). The polyamic acid-polyimide had a number average molecular weight of about 8500.

(polymerization example 11)

Make the CBDA of 0.18g (0.93mol) and the DA-11 of 0.78g (1.0mmol) in NMP (8.71g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-11 ). The polyamic acid-polyimide had a number average molecular weight of about 9600.

(polymerization example 12)

Make the CBDA of 0.18g (0.93mol) and the DA-12 of 0.57g (1.0mmol) in NMP (6.78g), react 16 hours at room temperature, prepare polyamic acid-polyimide polymerization solution (PI-12 ). The polyamic acid-polyimide had a number average molecular weight of about 11,200.

<Measurement of Solubility of Polyamic Acid-Polyimide>

(Example 10)

Add BCS to 3 g of polyamic acid-polyimide polymerization solution (PI-1) and stir to prepare solution (A-1) so that polyamic acid-polyimide becomes 6% by mass, NMP becomes 54% by mass, BCS became 40 mass %, and the solubility of the polyamic-acid-polyimide at room temperature and freezing (-20 degreeC) was confirmed.

(Examples 11-19, Comparative Examples 3-4)

As shown in Table 2, the solubility of Examples 11-19 was confirmed by the method similar to Example 10. Moreover, about Comparative Examples 3-4, solubility was confirmed by the same method. In addition, solubility is shown by the following reference|standard.

○: No turbidity, precipitates, or gelation

△: Slightly cloudy

×: There is turbidity, precipitates, and gelation

[Table 2]

As shown in Table 2, it was confirmed that in Examples 10 to 19, the diamine compounds (DA-1 to DA-8, DA-11 to DA-12) of the present invention were polymerized and diluted with BCS as a poor solvent. The obtained polyamic acid-polyimide solution has no turbidity, precipitates, gelation, etc. in the varnish at room temperature or freezing (-20° C.), reflecting good solubility. On the other hand, in the polyamic acid-polyimide solutions of Comparative Examples 3 and 4, it was confirmed that turbidity, precipitates, gelation, etc. occurred in the varnish at room temperature and freezing (-20° C.). From the above, it was suggested that the solubility of the polymer can be improved by making the diamine compound when polymerizing polyamic acid-polyimide have the structure of the present invention.

Industrial availability

The diamine of the present invention and the polymer obtained therefrom can be easily imparted with various properties using inexpensive raw materials, and thus are expected to be useful in fields such as coatings and electronic materials, for example, as liquid crystal aligning films.

Claims (3)

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

R ¹ 、R ² 、R ³ and R ⁴ Each independently represents H or CH ₃ Wherein R is ¹ 、R ² 、R ³ And R ⁴ Must have one among them represent CH ₃ ，

W ₁ Represents a single bond or a phenylene group, the phenylene group is optionally substituted by a substituent group selected from the 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 2W ₁ Optionally 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,

W ₂ represents phenylene optionally substituted with a substituent selected from said group 1, 2W ₂ Optionally identical to or different from each other,

l represents a linear or branched alkylene group having 1 to 10 carbon atoms optionally substituted with a substituent selected from the group 1, wherein-CH in L ₂ Optionally selected from-O-) -NHCO-, -CONH-) -COO-, -OCO-) -NH-, -N (CH) ₃ ) <xnotran> -, -NHCONH-, -N (Boc) CONH-, -NHCON (Boc) -, -N (Boc) CON (Boc) -, -NHCOO-, -OCONH-, -CO-, -S-, -N (Boc) -, 2 , , 2 . </xnotran>

2. Diamine compound according to claim 1, characterized in that W is ₁ -L-W ₂ Is one of the following structures:

。

3. a method for producing a polymer from the diamine compound according to claim 1 or 2, the polymer being polyamic acid, polyamic acid ester, polyimide, polyurea, or polyamide.