KR20200044036A - New polymer and diamine compounds - Google Patents

Abstract

여기서 식 (1) 중, R¹, R², R³ 및 R⁴ 는 각각 독립적으로 H, CH₃ 또는 CF₃ 을 나타내고, 단, R¹, R², R³ 및 R⁴ 중, 반드시 하나는 CH₃ 또는 CF₃ 을 나타내고, W₁ 은, 단결합 또는 페닐렌을 나타내고, W₂ 는 페닐렌을 나타내고, L 은, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬렌기를 나타내고, 알킬렌의 CH₂ 는 산소 원자 등으로 치환되어 있어도 된다. 본 발명은, 입수성이 높은 원료를 사용함으로써, 각종 특성을 용이하게 부여하는 것이 가능한 디아민을 제공할 수 있고, 또한, 그것으로 부터 얻어지는 신규 중합체를 제공할 수 있다.The present invention relates to a diamine compound represented by the following general formula (1).

Here, in formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , provided that one of R ¹ , R ² , R ³ and R ⁴ is necessarily one CH ₃ or CF ₃ , W ₁ represents a single bond or phenylene, W ₂ represents phenylene, L represents a straight or branched chain alkylene group having 1 to 10 carbon atoms, and CH ₂ may be substituted with an oxygen atom or the like. The present invention can provide a diamine capable of easily imparting various properties by using a highly available raw material, and can also provide a novel polymer obtained therefrom.

Description

New polymer and diamine compounds

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

In general, polyimide resins are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display devices and semiconductors for their high mechanical strength, heat resistance, insulation properties, and solvent resistance. . In addition, recently, use as an optical communication material such as an optical waveguide material is also expected.

In recent years, developments in this field have been dazzling, and correspondingly, more and more advanced characteristics are required for the materials used. That is, it is expected that not only is it excellent in heat resistance and solvent resistance, but also has many performances according to the use.

However, polyimide, in particular, polyimide produced from pyromellitic anhydride (PMDA) and 4,4'-dioxyaniline (ODA), which are widely used as representative examples of all aromatic polyimide resins (kapton: trade name) Since it lacks solubility and cannot be used as a solution, it is obtained by heating and dehydrating through a precursor called polyamic acid.

Moreover, in the polyimide (hereinafter soluble polyimide) having solvent solubility, amide-based or lactone-based organic solvents such as N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone, which have been conventionally used in high solubility, are used. Because of its high boiling point, high temperature firing could not be avoided 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 have recently been conducted, and deterioration of element components becomes a problem when firing at a high temperature, so low temperature firing has recently been desired.

On the other hand, polyamic acid exhibiting high solvent solubility has a problem in that sufficient liquid crystal display properties are not obtained and volume change due to imidation is likely to occur, and polyimide soluble in organic solvents having a low boiling point is desired. .

As the solution, a method for synthesizing tetracarboxylic dianhydride using an alicyclic dicarboxylic anhydride which is advantageous for organic solvent solubility can be considered. As an example thereof, it is known to produce various acid dihydrides by using trimellitic anhydride or trimellitic anhydride as a raw material (for example, Patent Document 1).

On the other hand, as for the diamine, as in the above-mentioned acid anhydride example, a method of imparting various characteristics using inexpensive raw materials has not been known so far.

WO2006 / 129771 pamphlet

Several diamines having an imide ring have been reported so far, but it has been pointed out that the diamine does not dissolve or the molecular weight does not increase because all have low solubility.

The present invention provides a high-solution-soluble diamine capable of easily imparting various properties not obtained by imidizing a polymer of a polyamic acid obtained from a diamine and an acid anhydride by using a commercially available raw material that is inexpensive and highly available. It aims at providing the manufacturing method and the diamine obtained, and the novel polymer obtained from it.

The present inventors conducted diligent investigations to solve the above problems, and as a result, diamines and acids 2 were used as raw materials using conventional diamine compounds having a straight chain or branched chain alkylene group and commercially available compounds with high availability. The method of producing a polymer capable of easily imparting various properties that cannot be obtained without imidizing the polymer of the polyamic acid obtained from the anhydride was completed, and the invention was completed.

This invention is based on this knowledge, and makes the following a summary.

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

[Formula 1]

In equation (1),

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ with the proviso that one of R ¹ , R ² , R ³ and R ⁴ must always be CH ₃ or CF ₃ Represents,

W ₁ represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the first group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, and a Boc-protected amino group, and the two W ₁ may be the same or different from each other,

W ₂ represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W ₂ may be the same or different from each other,

L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH ₂ -in L represents -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 It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atoms are not bonded to each other.

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

By using the liquid crystal aligning agent containing the polymer of the present invention, a liquid crystal aligning film having high voltage retention and rubbing resistance and capable of quickly alleviating accumulated charges, and a liquid crystal display device having excellent display characteristics are provided.

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

Moreover, the liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer obtained from the diamine which has the structure represented by said Formula (1) (it is also hereafter referred to as a specific polymer).

Hereinafter, each condition is explained in full detail.

<Specific diamine>

As described above, the diamine compound according to the present invention is represented by formula (1). Here, each substituent of formula (1) is defined as follows.

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , provided that one of R ¹ , R ² , R ³ and R ⁴ necessarily represents CH ₃ or CF ₃ ,

W ₁ represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the first group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, and a Boc-protected amino group, and the two W ₁ may be the same or different from each other,

W ₂ represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W ₂ may be the same or different from each other,

L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH ₂ -in L represents -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 It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the 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 , provided that one of R ¹ , R ² , R ³ and R ⁴ necessarily represents CH ₃ or CF ₃ .

Among them, R ¹ and R ⁴ represent CH ₃ or CF ₃ , preferably R ² and R ³ represent a hydrogen atom, more preferably R ¹ and R ⁴ represent a methyl group, and R ² and R ^{3 It} is preferable from the viewpoint of high solubility to represent a hydrogen atom.

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

As W ₂ , a 1,4-phenylene group is preferable.

As the alkylene having 1 to 10 carbon atoms, L may be straight or branched, and straight-chain alkylene represented by-(CH ₂ ) _n- (where n is 1 to 10) or 1-methyl Methane-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-methylpentane- 1,5-diyl, 1-ethylpentane-1,5-diyl, 1-propylpentane-1,5-diyl, 2-methylpentane-1,5-diyl, 2-ethylpentane-1,5-diyl, 2-propylpentane-1,5-diyl, 3-methylpentane-1,5-diyl, 3-ethylpentane-1,5-diyl, 3-propylpentane-1,5-diyl, 1-methylhexane-1 , 6-diyl, 1-ethyl Hexane-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 And branched alkylenes such as -1,1-diyl, 1-phenylethane-1,2-diyl, and 1-phenylpropane-1,3-diyl.

These straight chain or branched alkylene (-CH _2- ) is -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- , may be substituted with a group selected from the second group which is a piperidine ring and a piperazine ring.

However, at this time, groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atom are not bonded. In other words, when there are a plurality of groups selected from the second group capable of substituting the alkylene, when the bonding portion between the groups selected from the second group is bonded to the same atom except the carbon atom, the second group The military selected from the military cannot be adjacent to each other. If the bonding portion between groups selected from the second group is carbon atoms or is bonded to each other with different atoms, groups selected from the second group can be bonded. Preferably, if the bonding portion between groups selected from the second group is between carbon atoms, groups selected from the second group can be bonded.

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

In a preferred structure of the W ¹ -LW ² is, there can be the following structure, and is not limited to these.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

<Method for producing a specific diamine>

Below, the method of obtaining the above-mentioned diamine is demonstrated.

Although the method for synthesizing the specific diamine of the present invention is not particularly limited, for example, a bismaleimide compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted to represent the following formula (C). After the compound is obtained, a method of imidizing this to obtain a compound represented by the following formula (D) and converting it into a compound represented by the formula (1) can be given.

[Formula 9]

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

As the protecting group (Pro) of the amino group, acetyl group, trifluoroacetyl group, pivaloyl group, tert-butoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, benzyloxy Carbonyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, 9-fluorenyl methyloxycarbonyl group, phthaloyl group, allyloxycarbonyl group, p- A toluene sulfonyl group, o-nitrobenzenesulfonyl group, and the like can be used, but are not limited to these.

The amount of the compound represented by the formula (B) is preferably 2 mol to 4 mol, more preferably 2 mol to 2.5 mol, per 1 mol of the compound represented by the formula (A). By making the compound represented by Formula (B) an excess amount, the reaction can proceed smoothly and further, by-products can be suppressed.

This reaction is preferably carried out in a solvent.

The solvent can be used without limitation as long as it is a solvent that 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, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile, and butyronitrile; Etc. can be used.

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

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

The reaction temperature is not particularly limited, but is in the range from -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 reacted, if necessary, in the presence of an inorganic base or an organic base.

Examples of the base used for the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; bases such as tert-butoxy sodium, tert-butoxy potassium, sodium hydride and potassium hydride; An amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline or collidine can be used. Especially, triethylamine, pyridine, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride, etc. are preferable.

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

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

In the case of imidization, chemical imidization is simple, in which a catalyst is added to a solution of the compound represented by formula (C) obtained by reaction of an amine component with a bismaleimide compound. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature, and the decomposition of the Pro group does not easily occur in the process of imidization.

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. As for the organic solvent used in this reaction, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. are preferable from solubility, and these are used alone or in combination of two or more. May be

The concentration of the compound is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the compound does not easily occur.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has basicity suitable for advancing the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction.

The temperature at the time of performing the imidization reaction is -20 to 140 deg. C, preferably 0 to 100 deg. C, and the reaction time can be carried out in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole of the amic acid group, preferably 2 to 20 times mole, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 to 30 times mole of the amic acid group.

When Q is NO ₂ , conditions for producing a specific diamine represented by Formula (1) by reducing the compound represented by Formula (D) are described below.

The catalyst used for the reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. Moreover, it is not necessary to necessarily be a metal catalyst of activated carbon supported type such as palladium hydroxide, platinum oxide, or Raney nickel. Palladium-activated carbon, which is generally widely used, is preferable because good results can be obtained.

These reactions are carried out under a hydrogen atmosphere, normal pressure, or pressurized conditions. Moreover, you may perform reduction of a nitro group using metals, such as iron, tin, zinc, or these metal salts with a proton source. The metal and the metal salt may be used alone or in a mixture of two or more.

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

In order to advance the reduction reaction more effectively, the reaction may be carried out in the presence 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 mass%, more preferably 10 to 20 mass% with respect to the dinitro compound (D). Moreover, in order to advance a reduction reaction more effectively, a reaction may be performed under pressure. In this case, in order to avoid reduction of the benzene nucleus, it is carried out in a pressure range up to 20 atmospheres. Preferably, the reaction is carried out in a range up to 10 atmospheres.

The solvent can be used without limitation as long as it is a solvent that 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; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile, and butyronitrile; Alcohols such as methanol and ethanol; Etc. can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent may be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.

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

The reaction temperature is not particularly limited, but is in the range from -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.

When Q is a protected amine (NHPro), conditions under which the compound represented by formula (D) is deprotected to produce a specific diamine represented by formula (1) are described below.

Although it does not specifically limit as a method of deprotection of a protecting group, In the presence of an acid or a base, it is possible to obtain a target object by neutralizing after hydrolysis. Examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid. Examples of the base used include sodium hydroxide and sodium hydrogen carbonate , Inorganic bases such as potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine , Organic amines such as quinoline and collidine. Moreover, you may perform deprotection using a Lewis acid compound, such as aluminum chloride and a trifluoroborane-diethyl ether complex. Moreover, you may perform a debenzylation reaction in a hydrogen atmosphere. Further, an acid, an inorganic base, or an ammonium salt containing fluorine such as hydrofluoric acid, cesium fluoride, potassium fluoride, tetrabutylammonium fluoride, or the like may be used.

As for the solvent, any solvent that does not interfere with hydrolysis can be used, and aprotic polar organic solvents such as DMF, DMSO, DMAc, NMP, Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, D Ethers such as oxane, aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, chloroform, dichloro Halogen-based hydrocarbons such as methane, carbon tetrachloride, and dichloroethane, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc., nitriles (lower fatty acid esters such as acetonitrile, propionitrile, butyronitrile, methanol, ethanol) , 1-propanol, 2-propanol, 1-butanol, alcohols, or water may be used, and these solvents may be appropriately selected in consideration of easy reaction, etc. , The above solvents may be used alone or in combination of two or more, and may be used as a non-aqueous solvent by using a suitable dehydrating agent or drying agent in consideration of the use of Lewis acid or the like.

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

[Preparation of formula (B)]

Of the compounds represented by the formula (B), the compound (B1) wherein Q is NHPro is obtained by reacting the diamine represented by the following formula (B1-1) with an acid chloride of an amine protecting group (Pro) or an acid anhydride. . At this time, the diamine (B1-1) is preferably a symmetric diamine from the viewpoint of suppressing the complexity of the reaction. In the formula, W ₁ , W ₂ , L, and Pro represent the above meaning.

[Formula 10]

As (Pro) -Cl, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t-butyl chloroformate, benzyl chloroformate, benzyl chloroform Acid-9-fluorenyl, acetyl chloride, trifluoroacetyl chloride, pivaloyl chloride, tert-butoxycarbonyl chloride, ethoxycarbonyl chloride, isopropoxycarbonyl chloride, 2,2,2-triclo Loethoxycarbonylchloride, benzyloxycarbonylchloride, trimethylsilylchloride, triethylsilylchloride, dimethylphenylsilylchloride, tert-butyldimethylsilylchloride, tert-butyldiethylsilylchloride, 9-fluorenylmethyloxycar Carbonyl chloride, phthaloyl chloride, allyloxycarbonyl chloride, p-toluenesulfonyl chloride, o-nitrobenzenesulfonylchlora Id and the like, but are not limited to these.

Examples of (Pro) ₂ O include, but are not limited to, dimethyl dicarbonate, diethyl dicarbonate, dit-butyl dicarbonate, dibenzyl dicarbonate, and the like.

The reaction for obtaining the compound represented by the formula (B1) is preferably carried out in the presence of a base. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate; Amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine; Sodium hydride, potassium hydride, tert-butoxy sodium, tert-butoxy potassium, and the like can be used. When using a base, it is preferable to use amines in consideration of the operability of the post-treatment of the reaction.

As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the desired reaction can be used. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, and N-methylpyrrolidone; Ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitrile, such as acetonitrile, propionitrile, and butyronitrile, etc. can be used.

These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. The said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent or drying agent.

The reaction temperature is preferably from -100 ° C or higher to a temperature range from the boiling point temperature of the reaction solvent to be 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 the formula (2) obtained by the reaction formula (1) may be purified by column chromatography such as distillation, recrystallization, or silica gel, but may be used in the next step without purification.

Of the compounds represented by the formula (B), the compound (B2) wherein Q is NO ₂ is obtained by deprotecting the compound represented by the following formula (B2-1). As a condition for deprotection, the above method can be used. In the formula, W ₁ , W ₂ , L, and Pro represent the above meaning.

[Formula 11]

Moreover, the compound represented by Formula (B2-1) is halogenated and sulfonylated with the following Formula (B2-3) {methanesulfonyl (OMs), ethanesulfonyl (OEs), p-toluenesulfonyl (OTs), Trifluoromethanesulfonyl (OTf), etc.} and a nitrated phenol represented by the following formula (B2-4). In the formula, W ₁ and W ₂ represent the above meaning, and L ¹ represents alkylene in which one CH ₂ (strictly substituted CH ₂ ) is removed from L.

[Formula 12]

The compound represented by formula (B2-3) used as a starting material in the reaction of this step, and the nitrated phenol represented by formula (B2-4) can be obtained as a commercial product or can be produced by a known method.

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

It is preferable to perform reaction in 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, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, potassium phosphate, and 1,8-diazabi 1-4 equivalents can be used with respect to the compound represented by Formula (B2-3), such as an organic base, such as cyclo [5,4,0] -7-undecene.

Especially, alkali metal carbonates, such as sodium carbonate and potassium carbonate, are preferable. Particularly, the use of fine powdered potassium carbonate is preferred because it improves reactivity. 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), and N-methylpyrrolidone are preferred. And N-methylpyrrolidone is particularly preferred.

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

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

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

The target product in each step obtained by each of the above reactions may be purified by column chromatography such as distillation, recrystallization, or silica gel, or may be provided in the next step without being purified and remaining as a reaction solution.

<Polymer>

The polymer of the present invention is a polymer obtained using the diamine. As a specific example, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. are mentioned.

<Diisocyanate component>

As a diisocyanate component which gives a polyamide by reaction with the diamine represented by the 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) contains a structure containing an aromatic ring. Moreover, an aliphatic diisocyanate means that the group Y of the said isocyanate structure consists of a cyclic or acyclic aliphatic structure.

Specific examples of the aromatic diisocyanate include o-phenylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, toluene diisocyanates (e.g., tolylene 2,4-diisocyanate), 1,4 -Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 2,2'-bis (4-diisocyanate phenyl) propane, 4,4'-diisocyanate diphenylmethane, 4 And 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, and 2,2'-diisocyanate benzophenone. . As aromatic diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene 2,4-diisocyanate is preferably mentioned.

As a specific example of aliphatic diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, etc. are mentioned. As an aliphatic diisocyanate, isophorone diisocyanate is mentioned preferably. Among them, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferred from the viewpoint of polymerization reactivity, and isophorone diisocyanate is more preferred from the viewpoint of availability and polymerization reactivity.

<Tetracarboxylic dianhydride>

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

[Formula 13]

X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X ₁ in the polyimide precursor is required such as solubility in a solvent of a polymer and coating properties when used as a liquid crystal aligning agent, alignment property of a liquid crystal when used as a liquid crystal aligning film, voltage retention, and accumulated charge. It is appropriately selected according to the degree of properties, and may be one kind of the same polymer, or two or more kinds may be mixed.

If deliberately shows a specific example of X _1, it can be given a structure such as the formula (X-1) ~ (X -46) is placed in 13 ~ 14 of International Publication No. 2015/119168.

In the following, represents the structure of a preferred X _1, the present invention is not limited to these.

[Formula 14]

<Dicarboxylic acid>

Specific examples of the monomer compound for constructing a dicarboxylic acid component that provides a polyamide by reaction with the diamine represented by the general formula (1) are terephthalic acid, isophthalic acid, 2-methyl-isophthalic acid, 4- Methyl-isophthalic acid, 5-methyl-isophthalic acid, 5-allyloxyisophthalic acid, 5-allyloxycarbonylisophthalic acid, 5-propagyloxyisophthalic acid, 5-acetyloxyisophthalic acid, 5-benzoylamide isophthalic acid, Tetrafluoroisophthalic acid, methyl terephthalic acid, tetrafluoro terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 1,6-anthracenedicica Leic acid, 4,4'-dicarboxybiphenyl, 3,4'-dicarboxybiphenyl, 2,3'-dicarboxybiphenyl, 2,4'-dicarboxybiphenyl, 4,4'-di Carboxydiphenyl ether, 3,4'-dicarboxydiphenyl ether, 2,3'-dicarboxydiphenyl ether, 2,4'-dicarboxydipe 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'-dimethoxy-4,4'-dicarboxybiphenyl, 4,4'-dimethoxy-3,3'-dicarboxybiphenyl, 2,2'-dimethoxy-4,4'-dicarboxybiphenyl, 4,4'-dicarboxybenzophenone, 3,4'-dicarboxybenzophenone, 3,3'-dicarboxybenzophenone, 4, 4'-dicarboxydiphenylmethane, 3,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylamide, 3,4-dicarboxydiphenyl Amide, 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) formamide, N- [4 {(4-carboxyphenyl) carbo Amino} 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-carboxyphenyl) hexafluoropropane, 2,2'-bis [4- (4-carboxyphenoxy) phenyl] hexa Fluoropropane, 1,5-bis (4-carboxyphenyl) pentane, 1,4-bis (4-carboxyphenyl) butane, 1,3-bis (4-carboxyphenyl) propane, 4,4'-di ( Carboxyphenyl) pentane-1,5-dioate, 4,4'-di (carboxyphenyl) hexane-1,6-dioate, 4,4'-di (carboxyphenyl) heptane-1,7-dioate, etc. And aromatic or aromatic-containing dicarboxylic acids, and acid halides and alkyl esters thereof.

Furthermore, 1,3-dicarboxycyclohexane, 1,4-dicarboxycyclohexane, 1,2-dicarboxycyclobutane, 1,3-dicarboxycyclobutane, bis (4-carboxycyclohexyl) methane, bis ( Alicyclic dicarboxylic acids such as 4-carboxy-3-methylcyclohexyl) methane, bis (4-carboxycyclohexyl) ether, bis (4-carboxy-3-methylcyclohexyl) ether and acid halides thereof, and Alkyl esterification is mentioned, and mixtures of two or more of these can also be used.

In obtaining the polymer of the present invention by polymerization reaction with a diamine component containing the diamine compound represented by the formula (1), a known synthetic technique can be used. In general, it is a method of reacting at least one member selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component and a diamine component in an organic solvent. The reaction of at least one selected from a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component and a diamine component proceeds relatively easily in an organic solvent, and is advantageous in that by-products do not occur.

The organic solvent used for the reaction of at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component and the diamine component is not particularly limited as long as the resulting polymer is dissolved. The specific example is given below.

Examples of the organic solvent usable here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamylketone, methylnonylketone, methylethylketone, methylisoamylketone, 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, diethyl 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, di Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, Amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, 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, methyl pyruvate, ethyl pyruvate, 3-methoxypropionate methyl, 3-ethoxypropionate methylethyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N -Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination.

Moreover, since moisture in the organic solvent causes the polymerization reaction to be inhibited, it is preferable to use a dehydrated and dried organic solvent as much as possible.

When reacting at least one type selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component with a diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the diisocyanate component , A method of adding at least one selected from the dicarboxylic acid component and the tetracarboxylic acid component as it is or by dispersing or dissolving it in an organic solvent, conversely, in the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component A method of adding a diamine component to a solution in which at least one selected substance is dispersed or dissolved in an organic solvent, alternately adding at least one selected from diisocyanate component, dicarboxylic acid component and tetracarboxylic acid component and diamine component How to do it, etc., any of these methods The. Moreover, when at least 1 type selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic-acid component or a diamine component consists of multiple types of compounds, you may react in a pre-mixed state, or may react individually individually. Alternatively, the low-molecular-weight substances reacted individually may be mixed to make a high-molecular-weight substance.

The polymerization temperature at that time can be any temperature of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, and thus the diisocyanate component , The total concentration in the reaction solution of at least one selected from the dicarboxylic acid component and the tetracarboxylic acid component and the diamine component is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The initial reaction is carried out at a high concentration, and thereafter, an organic solvent can be added.

In the polymerization reaction of the polymer of the present invention, the ratio of the total number of moles of at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component to the total mole number of the diamine component is preferably 0.8 to 1.2. Do. As with the conventional polycondensation reaction, the closer this mole ratio is to 1.0, the greater the molecular weight of the resulting polymer.

When the produced polymer is recovered from the reaction solution of the polymer of the present invention, the reaction solution may be introduced into a poor solvent and precipitated. Poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by being introduced into the poor solvent is collected by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, if the operation of reprecipitating and recovering the polymer precipitated and reprecipitating and recovering it is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more poor solvents selected from these is preferable since the efficiency of purification is further improved.

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

[Formula 15]

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

[Formula 16]

In the formula (A2), R ¹ , R ² , R ³ , R ⁴ , W ₁ , W ₂ , and L represent the above meaning, C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Each may be the same or different.)

In the formula [1], A ₁ and A ₂ may each be one type and a polymer having the same repeating unit, or may be a polymer in which A ₁ or A ₂ are plural and have repeating units having different structures.

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

According to a preferred embodiment of the present invention, A ₁ is preferably a group derived from the preferred diisocyanate component exemplified above.

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

[Formula 17]

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

Specific examples of the alkyl group for R ₁₁ include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Can be mentioned. From the viewpoint of easy imidization by heating, R ₁₁ is preferably a hydrogen atom or a methyl group.

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

[Formula 18]

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

Moreover, when manufacturing the polymer of this invention, 2 or 3 types of diisocyanate component, dicarboxylic acid component, and tetracarboxylic acid component may be reacted simultaneously or sequentially, for example, diisocyanate component and tetra When the carboxylic acid component is reacted, a polyurea polyamic acid that is a polymer having a repeating unit represented by the formula [1] and a repeating unit represented by the formula [2] is obtained.

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the method shown below.

Specifically, it is synthesized by reacting tetracarboxylic dianhydride and diamine at -20 to 150 ° C, preferably 0 to 70 ° C, in the presence of an organic solvent for 30 minutes to 24 hours, preferably 1 to 12 hours. can do.

The organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. from the solubility of monomers and polymers. You may mix and use the above.

The concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur easily and the high molecular weight body is easily obtained.

The polyamic acid obtained as described above can be recovered by depositing a polymer by injecting the reaction solution into a poor solvent while stirring well. Moreover, the powder of the purified polyamic acid can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited, and examples include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, and toluene. Water, methanol, ethanol, 2-propanol, and the like are preferred.

<Method for producing polyimide>

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

When polyimide is prepared from polyamic acid, chemical imidation is simple by adding a catalyst to the solution of the polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature, and the molecular weight of the polymer does not easily decrease in the course of imidization.

Chemical imidation can be performed by stirring the polymer to be imidized in the presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has basicity suitable for advancing the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction.

The temperature at the time of performing the imidization reaction is -20 to 140 deg. C, preferably 0 to 100 deg. C, and the reaction time can be carried out in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole of the polyamic acid group, preferably 2 to 20 times mole, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 to 30 times mole of the polyamic acid group. The imidation rate of the obtained polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.

Since the added catalyst or the like remains in the solution after the imidization reaction of the polyamic acid, the obtained imidized polymer is recovered by the means described below, and redissolved with an organic solvent to obtain a liquid crystal aligning agent of the present invention. desirable.

The solution of the polyimide obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. Precipitation is carried out several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polymer powder.

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

<Preparation of polyimide precursor-polyamic acid ester>

The polyamic acid ester which is a polyimide precursor used in the present invention can be produced by the production method of (i), (ii) or (iii) shown below.

(i) When prepared from polyamic acid

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

As the esterifying agent, it is preferable that it can be easily removed by purification, N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamidedineopentylbutylacetal, N, N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriagene, 1-ethyl-3-p-tolyltriagene , 1-propyl-3-p-tolyltrigen, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. The amount of the esterifying agent added is preferably 2 to 6 molar equivalents to 1 mole of the repeating unit of the polyamic acid.

Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide , Dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] to formula [ D-3] can be used.

[Formula 19]

In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ Represents a C1-C4 alkyl group.

These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not melt | dissolve a polyimide precursor, you may use it in the range in which the produced | generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since moisture in the solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, it is preferable to use a solvent that is dehydrated and dried.

The solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these are mixed one or two or more. You may use it. 1-30 mass% is preferable and 5-20 mass% is more preferable at the concentration at the time of manufacture in that precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain.

(ii) When prepared by reaction of tetracarboxylic acid diester dichloride and diamine

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

Specifically, tetracarboxylic acid diester dichloride and diamine are present at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of a base and an organic solvent, for 30 minutes to 24 hours, preferably 1 to It can be prepared by reacting for 4 hours.

Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the base, but pyridine is preferred for the reaction to proceed gently. It is preferable that it is 2-4 times mole with respect to the tetracarboxylic-acid diester dichloride because the addition amount of a base is an amount which is easy to remove and a high molecular weight body is easy to obtain.

The solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of monomers and polymers, and these may be used alone or in combination of two or more. 1-30 mass% is preferable, and 5-20 mass% is more preferable at the point of a polymer concentration at the time of manufacture that precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain. Moreover, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the production of the polyamic acid ester is desirably dehydrated as much as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere.

(iii) When prepared from tetracarboxylic acid diesters and diamines

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

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

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, and dimethoxy-1 , 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluroniumtetrafluoroborate, O- (benzotriazole- 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl) diphenyl phosphonate, etc. can be used You can. The amount of the condensing agent added is preferably 2 to 3 times the mole relative to the tetracarboxylic acid diester.

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

In addition, in the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halide such as lithium chloride and lithium bromide is preferred. The amount of Lewis acid added is preferably 0 to 1.0 times mole relative to the diamine component.

Among the above three methods for producing polyamic acid esters, the production method of (i) or (ii) is particularly preferred because a high molecular weight polyamic acid ester is obtained.

The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. The powder of the purified polyamic acid ester can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

In order to manufacture the polymer of the present invention, in the above production method, a diamine represented by formula (1) may be used as the diamine. Moreover, in that case, what is other than what is represented by Formula (1) can be used as diamine. If the specific example is shown, diamine in which two amino groups are bonded to the structure of formula (2) shown in paragraph 4 of international publication 2015/119168, and formula (Y-1) shown in paragraphs 8 to 12 ) To (Y-97), diamines in which two amino groups are bonded to the structures of formulas (Y-101) to (Y-118); Diamine of formula (2) published in paragraph 6 of international publication 2013/008906; Diamine of formula (1) published in paragraph 8 of international publication 2015/122413; A diamine in which two amino groups are bonded to the structure of formula (3) shown in paragraph 8 of International Publication No. 2015/060360; Diamine of formula (1) described in 8 of Unexamined-Japanese-Patent No. 2012-173514; And diamines of formulas (A) to (F), which are published in paragraph 9 of International Publication No. 2010-050523.

The polymer of the present invention thus obtained can be used as a coating material, and can also be used in applications such as an insulating film, a film substrate, a liquid crystal alignment film, and a protective film.

Example

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.

The structure of the diamine compound used in Examples is shown below.

<Diamine compound>

[Formula 20]

[Formula 21]

[Formula 22]

DA-1 to DA-8 and DA-10 to DA-15 are novel, unpublished compounds such as literatures, and their synthesis methods are described in detail in Synthesis Examples 1 to 14 below.

DA-9 was synthesized by the synthetic method described in Patent Document (WO2017-057854).

The abbreviation of the organic solvent used in Examples etc. is as follows.

NMP: N-methyl-2-pyrrolidone.

BCS: Butyl cellosolve.

THF: Tetrahydrofuran.

DMF: N, N-dimethylformamide.

CH ₂ Cl ₂ : dichloromethane.

CHCl ₃ : 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 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 material: Tetramethylsilane (TMS).

(Synthesis Example 1)

Synthesis of [DA-1]:

[Formula 23]

4-[(4-aminophenoxy) methoxy] aniline (230.0 g, 999 mmol) and THF (1600 g) were added to a 3 liter 4-neck flask, and di-tert-dicarbonate was added in a water bath. Butyl (218.0 g, 999 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, and the obtained residue was isolated 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 added to a 3 L 4-neck flask, and 1,3-DMCBDA (40.4 g, 180 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (85.5 g, 1081 mmol) and acetic anhydride (55.2 g, 540 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (5 L), and the precipitate was separated by filtration. 180.1 g of [DA-1-2] was obtained by adding MeOH (2 L) to the obtained crude product and repulsing washing at room temperature.

[DA-1-2] (169.8 g, 200 mmol) and CH ₂ Cl ₂ (2500 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (204.1 g, 1000 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (3 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, and THF (500 g) and MeOH (700 g) were added to the obtained crude product, and repulping and washing at room temperature gave 106.0 g of [DA-1] (white solid). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-1].

(Synthesis Example 2)

Synthesis of [DA-2]:

[Formula 24]

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

[DA-2-1] (46.4 g, 129 mmol) and NMP (460 g) were added to a 3 L 4-neck flask, and 1,3-DMCBDA (14.5 g, 65 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Then, pyridine (30.7 g, 388 mmol) and acetic anhydride (19.8 g, 194 mmol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 41.1 g of [DA-2-2] was obtained by adding MeOH (400 mL) to the obtained crude product, and washing by repulping at room temperature.

[DA-2-2] (41.1 g, 45 mmol) and CH ₂ Cl ₂ (600 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (46.4 g, 454 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, and EtOH (100 g) was added to the obtained crude product, followed by repulsing and washing at room temperature to obtain 25.3 g of [DA-2] (white solid). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-2].

(Synthesis Example 3)

Synthesis of [DA-3]:

[Formula 25]

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

[DA-3-1] (48.0 g, 120 mmol) and NMP (480 g) were added to a 3 L 4-neck flask, and 1,3-DMCBDA (13.4 g, 60 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (28.4 g, 360 mmol) and acetic anhydride (18.4 g, 180 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 42.5 g of [DA-3-2] was obtained by adding MeOH (400 mL) to the obtained crude product, and repulsing washing at room temperature.

[DA-3-2] (42.5 g, 43 mmol) and CH ₂ Cl ₂ (640 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (43.9 g, 430 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, MeOH (100 g) was added to the obtained crude product, and re-pulping and washing at room temperature yielded 26.3 g of [DA-3] (purple solid). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-3].

(Synthesis Example 4)

Synthesis of [DA-4]:

[Formula 26]

N-Boc-2- (4-aminophenyl) ethanol (158.7 g, 669 mmol), triethylamine (135.4 g, 1338 mmol) and THF (1100 g) were added to a 2 L 4-neck flask, and water bath Among them, ethanesulfonyl chloride (128.9 g, 1003 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (3 L), and extraction was performed using pure water (1 L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 224.2 g of [DA-4-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.

In a 3 ℓ 4-neck flask [DA-4-1] (217.3 g, 660 mmol), 4-nitrophenol (101.0 g, 726 mmol), potassium carbonate (136.8 g, 990 mmol), NMP (1200 g ) And stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (2 L), and neutralized with an aqueous 1N-hydrochloric acid 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, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off with a rotary evaporator, IPA (400 g) was added, and repulsing and washing at room temperature gave 164.8 g of [DA-4-2].

[DA-4-2] (84.3 g, 226 mmol), 6N-hydrochloric acid aqueous solution (200 g) and ethyl acetate (600 g) were added to a 2 L 4-neck flask and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1.2 L), and neutralized with an aqueous 1N-sodium hydroxide 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, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 60.8 g of [DA-4-3] was obtained by distilling off the obtained filtrate using a rotary evaporator.

[DA-4-3] (60.8 g, 235 mmol) and NMP (600 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (24.8 g, 111 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (55.8 g, 705 mmol) and acetic anhydride (35.9 g, 352 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 79.1 g of [DA-4-4] was obtained by adding EtOH (1000 g) to the obtained crude product and repulsing washing at room temperature.

[DA-4-4] (79.0 g, 112 mmol) and DMF (800 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (7.9 g) was added, followed by hydrogen. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was distilled off with a rotary evaporator, ethyl acetate (1500 g) was added, and repulping and washing at room temperature gave 69.9 g of [DA-4] (white solid). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-4].

(Synthesis Example 5)

Synthesis of [DA-5]:

[Formula 27]

[DA-4-2] (80.6 g, 216 mmol), THF (300 g), and EtOH (100 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.0 g) ) Was added, and the mixture was hydrogen-substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. 73.9 g of [DA-5-1] was obtained by distilling off the obtained filtrate with a solvent by a rotary evaporator.

[DA-5-1] (73.9 g, 225 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (23.7 g, 106 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (53.4 g, 675 mmol) and acetic anhydride (34.5 g, 338 mol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. EtOH (1000 g) was added to the obtained crude product, and 85.4 g of [DA-5-2] was obtained by repulsing and washing at room temperature.

[DA-5-2] (85.4 g, 101 mmol), 6N-hydrochloric acid aqueous solution (200 g) and ethyl acetate (800 g) were added to a 2 L 4-neck flask, and the mixture was stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (1.2 L) and neutralized with triethylamine. The precipitate was separated by filtration, ethyl acetate (1500 g) was added, and repulping and washing at room temperature gave 61.1 g of [DA-5]. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-5].

(Synthesis Example 6)

Synthesis of [DA-6]:

[Formula 28]

3- (4-tert-butoxycarbonylaminophenyl) propanol (237.3 g, 944 mmol), triethylamine (190.0 g, 1888 mmol), THF (1000 g) was added to a 2 L 4-neck flask. , Ethanesulfonyl chloride (182.0 g, 1416 mmol) was added dropwise in a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (2 L), and extraction was performed using pure water (1 L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 324.2 g of [DA-6-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.

In a 3 ℓ 4-neck flask [DA-6-1] (324.2 g, 944 mmol), 4-nitrophenol (150.0 g, 1078 mmol), potassium carbonate (203.0 g, 1470 mmol), NMP (1700 g ) And stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (4 L) and neutralized with a 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, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off with a rotary evaporator, IPA (2000 g) was added, and repulsing and washing at room temperature yielded 173.4 g of [DA-6-2].

[DA-6-2] (86.7 g, 233 mmol), 6N-hydrochloric acid aqueous solution (180 g) and ethyl acetate (700 g) were added to a 2 L 4-neck flask, and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L), and neutralized with an aqueous 1N-sodium hydroxide 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, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 62.6 g of [DA-6-3] was obtained by distilling off the obtained filtrate using a rotary evaporator.

[DA-6-3] (62.6 g, 230 mmol) and NMP (900 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (25.5 g, 114 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (54.5 g, 690 mmol) and acetic anhydride (35.2 g, 345 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (4 L), and the precipitate was separated by filtration. 82.0 g of [DA-6-4] was obtained by adding MeOH (500 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-6-4] (80.0 g, 109 mmol) and DMF (3200 g) were added to a 5 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.0 g) was added, followed by hydrogen. Substituted and stirred at 60 ° C. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was distilled off with a rotary evaporator, ethyl acetate (1000 g) was added, and repulsed and washed at room temperature to obtain 59.1 g of [DA-6] (reddish-purple solid). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-6].

(Synthesis Example 7)

Synthesis of [DA-7]:

[Formula 29]

[DA-6-2] (86.7 g, 233 mmol), THF (350 g), and EtOH (90 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.7 g) ) Was added, and the mixture was hydrogen-substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. 65.8 g of [DA-7-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.

[DA-7-1] (65.8 g, 192 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (21.4 g, 96 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (45.6 g, 576 mmol) and acetic anhydride (29.8 g, 292 mol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 83.0 g of [DA-7-2] was obtained by adding MeOH (1000 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-7-2] (83.0 g, 96 mmol), 6N-hydrochloric acid aqueous solution (170 g) and ethyl acetate (700 g) were added to a 2 L 4-neck flask, and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L) and neutralized with triethylamine. The precipitate was separated by filtration, ethyl acetate (500 g) was added, and 25.2 g of [DA-7] was obtained by washing with repulping at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-7].

(Synthesis Example 8)

Synthesis of [DA-8]:

[Formula 30]

2- (4-nitrophenyl) ethylamine hydrochloride (50.0 g, 247 mmol), triethylamine (27.5 g, 271 mmol) and THF (500 g) were added to a 1 L 4-neck flask, and in a water bath, After adding 1,3-DMCBDA (27.1 g, 121 mmol), the mixture was stirred at room temperature for 6 h. After completion of the reaction, 67.2 g of [DA-8-1] was obtained by pouring the reaction system into pure water (1.5 L) and filtering the precipitate.

[DA-8-1] (67.2 g, 121 mmol) and acetic acid (400 g) were added to a 1 L 4-neck flask and stirred at 100 ° C. After the reaction was completed, the reaction system was poured into pure water (1.5 L), and the precipitate was separated by filtration. 30.4 g of [DA-8-2] was obtained by adding MeOH (60 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-8-2] (30.4 g, 58 mmol) and DMF (450 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (3.0 g) was added and hydrogen was added. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was poured into pure water (3 L), and the precipitate was separated by filtration. 25.9 g of [DA-8] (white solid) was obtained by adding MeOH (80 g) to the obtained crude product, and washing by repulping at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-8].

(Synthesis Example 9)

Synthesis of [DA-10]:

[Formula 31]

2- (4-nitrophenyl) ethylamine hydrochloride (25.0 g, 123 mmol), triethylamine (14.2 g, 140 mmol) and THF (250 g) were added to a 1 L 4-neck flask, and in a water bath, After adding 1,2,3,4-cyclobutanetetracarboxylic dianhydride (11.7 g, 60 mmol), the mixture was stirred at room temperature for 6 h. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. IPDA (500 g) was added to the obtained crude product, and 21.8 g of [DA-10-1] was obtained by repulsing and washing 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 added to a 1 L 4-neck 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 separated by filtration. 19.3 g of [DA-10-2] was obtained by adding MeOH (400 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-10-2] (19.3 g, 39 mmol) and DMF (400 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.0 g) was added and hydrogen was added. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was poured into pure water (3 L), and the precipitate was separated by filtration. 15.2 g of [DA-10] (white solid) was obtained by adding MeOH (300 g) to the obtained crude product and washing by repulping at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-10].

(Synthesis Example 10)

Synthesis of [DA-11]:

[Formula 32]

N, N'-bis [2- (4-aminophenyl) ethyl] urea (134.4 g, 450 mmol) and DMF (650 g) were added to a 1 liter 4-neck flask, and di-tert-dicarbonate was added in a water bath. Butyl (32.8 g, 150 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (1.5 L) was added, and the precipitate was separated by filtration. CHCl ₃ (1.5 L) was added to the obtained crude material, and the organic layer was washed with 10 wt% acetic acid aqueous solution (1.5 L). Further, 50.8 g of [DA-11-1] was obtained by neutralizing the organic layer with triethylamine, washing with pure water (2 L), and concentration.

[DA-11-1] (49.0 g, 123 mmol) and NMP (500 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (13.5 g, 60 mmol) was added in a water bath, Stir at room temperature for 6 h. Subsequently, pyridine (29.4 g, 369 mmol) and acetic anhydride (18.8 g, 185 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2.5 L), and the precipitate was separated by filtration. Subsequently, THF (800 g) was added to the obtained crude product, and after complete dissolution, it was concentrated until a solid precipitated at 40 ° C, MeOH (200 g) was added, and repulsed and washed at room temperature, [DA -11-2] to obtain 47.7 g.

[DA-11-2] (47.7 g, 48 mmol) and CHCl ₃ (480 g) were added to a 1 L 4-neck flask, and trifluoroacetic acid (55.7 g, 484 mmol) was added dropwise in a water bath. , And stirred at 50 ° C. After the reaction was completed, the reaction solution was poured into hexane (500 g), and the precipitate was separated by filtration. Next, MeOH (500 g) was added to the obtained crude product, neutralized with triethylamine, and the precipitate was separated by filtration. Subsequently, DMF (300 g) was added to the obtained crude product, and it was completely dissolved by heating to 60 ° C., and then concentrated until a solid precipitated at 40 ° C., THF (600 g) was added, and the mixture was removed at room temperature. 25.2 g of [DA-11] (white solid) was obtained by pulping and washing. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-11].

(Synthesis Example 11)

Synthesis of [DA-12]:

[Formula 33]

1- (4-nitrophenyl) -4-piperidineamine (39.0 g, 116 mmol) and NMP (400 g) were added to a 500 mℓ 4-neck flask, and 1,3-DMCBDA (12.8 g, After adding 47 mmol), the mixture was stirred at 50 ° C for 6 h. Subsequently, pyridine (27.6 g, 349 mmol) and acetic anhydride (17.8 g, 175 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. Subsequently, 32.1 g of [DA-12-1] was obtained by adding MeOH (250 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-12-1] (32.1 g, 51 mmol) and DMF (960 g) were added to a 2 L 4-neck flask, followed by nitrogen substitution, followed by addition of 5 wt% Pd / C (3.2 g), hydrogen Substituted and stirred at 50 ° C. After completion of the reaction, the reaction solution was separated by filtration, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained filtrate, and filtering with a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. In addition, 22.1 g of [DA-12] (light green solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-12].

(Synthesis Example 12)

Synthesis of [DA-13]:

[Formula 34]

4-amino-1-tert-butoxycarbonylpiperidine (70.0 g, 350 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (38.4 g, in a water bath). 171 mmol) and stirred at room temperature for 6 h. Subsequently, pyridine (82.9 g, 1049 mmol) and acetic anhydride (53.5 g, 524 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (3.5 L), and the precipitate was separated by filtration. Subsequently, 92.0 g of [DA-13-1] was obtained by adding MeOH (300 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-13-1] (92.0 g, 170 mmol) and CHCl ₃ (920 g) were added to a 2 L 4-neck flask, and trifluoroacetic acid (193.3 g, 1700 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After completion of the reaction, the precipitate was filtered off, ethyl acetate (300 g) was added to the obtained crude product, and repulping and washing at room temperature gave 97.8 g of [DA-13-2].

In a 1 ℓ 4-neck flask [DA-13-2] (40.0 g, 65 mmol), 2- (4-nitrophenyl) ethyl bromide (32.8 g, 143 mmol), potassium carbonate (35.9 g, 260 mmol) ), NMP (400 g) was added, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. 27.5 g of [DA-13-3] was obtained by adding MeOH (200 g) to the obtained crude product and washing by repulping at 60 ° C.

[DA-13-3] (29.3 g, 43 mmol) and DMF (900 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.9 g) was added, followed by hydrogen. Substituted and stirred at 60 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained crude product and filtering through a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Furthermore, 8.7 g of [DA-13] (skin solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-13].

(Synthesis Example 13)

Synthesis of [DA-14]:

[Formula 35]

Tert-butyl4- (4-aminophenyl) piperidine-1-carboxylate (22.8 g, 82 mmol) and NMP (230 g) were added to a 500 mℓ 4-neck flask and 1,3- in a water bath. After adding DMCBDA (8.9 g, 40 mmol), the mixture was stirred at room temperature for 6 h. Subsequently, pyridine (39.1 g, 494 mmol) and acetic anhydride (25.2 g, 247 mol) were added to the reaction solution and stirred at 50 ° C. After the reaction was completed, the reaction system was poured into pure water (1.5 L), and the precipitate was separated by filtration. Subsequently, 28.5 g of [DA-14-1] was obtained by adding MeOH (100 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-14-1] (28.5 g, 39 mmol) and CHCl ₃ (290 g) were added to a 500 mℓ 4-neck flask, and trifluoroacetic acid (43.9 g, 385 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After the completion of the reaction, the precipitate was separated by filtration, MeOH (150 g) was added to the obtained crude product, and repulping and washing at room temperature yielded [DA-14-2] of 29.2 g.

In a 1 ℓ 4-neck flask [DA-14-2] (28.5 g, 37 mmol), 2- (4-nitrophenyl) ethyl bromide (29.5 g, 111 mmol), triethylamine (30.0 g, 296 m Mol) and NMP (290 g) were added and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into pure water (2.5 L), and the precipitate was separated by filtration. 26.1 g of [DA-14-3] was obtained by adding MeOH (250 g) to the obtained crude product and washing by repulping at 60 ° C.

[DA-14-3] (26.1 g, 31 mmol) and DMF (800 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.6 g) was added and hydrogen was added. Substituted and stirred at 80 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained crude product and filtering through a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Moreover, 12.3 g of [DA-14] (skin solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-14].

(Synthesis Example 14)

Synthesis of [DA-15]:

[Formula 36]

Tert-butyl4- (4-aminophenyl) piperazine-1-carboxylate (33.2 g, 120 mmol) and NMP (330 g) were added to a 1 liter 4-neck flask, and 1,3-DMCBDA in a water bath. (13.1 g, 59 mmol) was added, followed by stirring at room temperature for 6 h. Subsequently, pyridine (28.4 g, 359 mmol) and acetic anhydride (18.3 g, 180 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. Subsequently, 40.7 g of [DA-15-1] was obtained by adding MeOH (150 g) to the obtained crude product, and repulsing washing at room temperature.

[DA-15-1] (40.7 g, 55 mmol) and CHCl ₃ (400 g) were added to a 2 L 4-neck flask, and trifluoroacetic acid (62.6 g, 548 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After completion of the reaction, the precipitate was separated by filtration, THF (200 g) was added to the obtained crude product, and 21.8 g of [DA-15-2] was obtained by repulsing and washing at 50 ° C.

[DA-15-2] (21.8 g, 28 mmol), 2- (4-nitrophenyl) ethyl bromide (14.3 g, 62 mmol), triethylamine (11.4 g, 113 m) in a 500 mℓ 4-neck flask Mol) and NMP (220 g) were added and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L), and the precipitate was separated by filtration. 17.9 g of [DA-15-3] was obtained by adding MeOH (200 g) to the obtained crude material and washing by repulping at 60 ° C.

[DA-14-3] (17.9 g, 21 mmol) and DMF (540 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (1.8 g) was added, followed by hydrogen. Substituted and stirred at 80 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (500 mL) to the obtained crude product and filtration through a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Further, 5.7 g of [DA-15] (skin color solid) was obtained by adding MeOH (50 g) to the obtained crude product, and repulsing and washing at 60 ° C. The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-15].

<Measurement of saturated solubility of diamine compound in NMP at room temperature>

(Example 1)

The diamine compound [DA-1] was added to NMP (2 g) heated to 60 ° C. until insoluble, and stirred at 60 ° C. for 1 hour. After heating, it was allowed to cool at room temperature for 6 hours, and the precipitate was removed to prepare a saturated NMP solution of [DA-1] at room temperature. Subsequently, a 1 wt% [DA-1] NMP solution was prepared as a sample, and the peak area was measured using HPLC. Finally, NMP (39 g) was added to the prepared saturated solution (1 g) to measure the peak area, and the saturated solubility of [DA-1] in NMP at room temperature was calculated.

(Examples 2 to 9 and Comparative Examples 1 to 2)

As shown in Table 1, Examples 2-9 were also calculated using the same method as in Example 1. Moreover, Comparative Examples 1-2 were computed by the same method.

As shown in Table 1, the saturation solubility of the diamine compounds (DA-1 to DA-8, DA-11) of the present invention in Examples 1 to 9 at room temperature is the diamine compounds of Comparative Example 1 It was confirmed that it showed good solubility compared with (DA-9). Moreover, it was also confirmed that the saturated solubility of the diamine compound (DA-8) of Example 8 in NMP at room temperature showed good solubility compared to the diamine compound (DA-10) of Comparative Example 2. From the above, it was suggested that the solubility in NMP can be improved by using the diamine compound as the structure of the present invention.

<Measurement of molecular weight of polymer>

The molecular weights of the polyimide, polyamic acid, and polyamic acid ester in Examples are normal temperature gel permeation chromatography (GPC) equipment (GPC-101) manufactured by Shodex Co., Ltd., and columns manufactured by Shodex (KD-803, KD-) 805) was measured as follows.

Column temperature: 50 ℃

Eluent: DMF (as an additive, lithium bromide-hydrate (LiBrH ₂ O) is 30 mmol / L, phosphoric anhydride (o-phosphoric acid) is 30 mmol / L, THF is 10 mL / L)

Flow rate: 1.0 ml / min

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

(Polymerization Example 1)

CBDA was reacted with 0.18 g (0.93 mol) and DA-1 with 0.64 g (1.0 mmol) in NMP (7.48 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-1). . This polyamic acid-polyimide had a number average molecular weight of about 29500.

(Polymerization Example 2)

CBDA was reacted with 0.18 g (0.93 mol) and DA-2 with 0.70 g (1.0 mmol) in NMP (7.98 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-2). . This polyamic acid-polyimide had a number average molecular weight of about 30000.

(Polymerization Example 3)

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

(Polymerization Example 4)

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

(Polymerization Example 5)

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

(Polymerization Example 6)

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

(Polymerization Example 7)

A polyamic acid-polyimide polymerization solution (PI-7) was prepared by reacting 0.18 g (0.93 mol) of CBDA with 0.67 g (1.0 mmol) of DA-7 in NMP (7.69 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 16900.

(Polymerization Example 8)

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

(Polymerization Example 9)

0.18 g (0.93 mol) of CBDA and 0.40 g (1.0 mmol) of DA-9 were reacted in NMP (5.28 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-9). . This polyamic acid-polyimide had a number average molecular weight of about 13600.

(Polymerization Example 10)

0.18 g (0.93 mol) of CBDA and 0.43 g (1.0 mmol) of DA-10 were reacted in NMP (5.53 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-10). . This polyamic acid-polyimide had a number average molecular weight of about 8500.

(Polymerization Example 11)

0.18 g (0.93 mol) of CBDA and 0.78 g (1.0 mmol) of DA-11 were reacted in NMP (8.71 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-11). . This polyamic acid-polyimide had a number average molecular weight of about 9600.

(Polymerization Example 12)

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

<Measurement of solubility of polyamic acid-polyimide>

(Example 10)

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

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

As shown in Table 2, the solubility of Examples 11 to 19 was confirmed using the same method as in Example 10. Moreover, solubility was confirmed also in Comparative Examples 3-4 by the same method. In addition, solubility is shown by the following criteria.

 ○: No cloudiness, precipitates, or gelation

 △: There is a small amount of turbidity

 ×: turbidity, precipitate, gelation

As shown in Table 2, the polyamic acid-polyyi obtained by polymerizing the diamine compounds (DA-1 to DA-8, DA-11 to DA-12) of the present inventions of Examples 10 to 19 and diluting them with poor solvent BCS. It was confirmed that the mid-solution exhibited good solubility without roominess, precipitate, gelling, etc., even at room temperature and freezing (--20 ° C). On the other hand, in the polyamic acid-polyimide solutions of Comparative Examples 3 and 4, at room temperature and freezing (--20 ° C), turbidity, precipitates, and gelation of the varnish were confirmed. From the above, it was suggested that the solubility of the polymer can be improved by making the diamine compound for polymerizing the polyamic acid-polyimide the structure of the present invention.

Industrial availability

Since the diamine of the present invention and the polymer obtained therefrom can easily impart various properties using inexpensive raw materials, usefulness is expected in fields such as paints and electronic materials, for example, liquid crystal alignment films.

Claims (2)

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

R ¹ , R ² , R ³ and R ⁴ each independently represent H, CH ₃ or CF ₃ , provided that one of R ¹ , R ² , R ³ and R ⁴ necessarily represents CH ₃ or CF ₃ ,
W ₁ represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, a Boc-protected amino group, and two W ₁ may be the same or different from each other,
W ₂ represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W ₂ may be the same or different from each other,
L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH ₂ -in L represents -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 It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atom are not bonded. A polymer obtained from the diamine compound represented by the formula (1) according to claim 1.