JP6059043B2 - Diaminomaleonitrile polymer and process for producing the same - Google Patents

Description

  The present invention relates to a diaminomaleonitrile polymer and a method for producing the same.

A polymer material containing nitrogen (hereinafter sometimes referred to as “nitrogen-containing polymer material”) having a repeating unit structure having a carbon double bond and a nitrile group, polyacrylonitrile (hereinafter referred to as “PAN”). Is known).
PAN is used as a raw material for fibers, films, and other various molded articles as a nitrogen-containing polymer material. In particular, PAN fibers have excellent mechanical performance, chemical resistance, light resistance, and the like, and are useful as clothing fibers, industrial fibers, carbon fiber precursors, and the like.
PAN is manufactured by a method of polymerizing acrylonitrile represented by the following formula (a) using a radical polymerization initiator or a basic catalyst, and the development of an anionic polymerization method for controlling a high degree of stereoregularity ( For example, the development of a radical polymerization method having a high average molecular weight with a uniform molecular weight (see, for example, Patent Document 2) has been reported.

  Similar to acrylonitrile, diaminomaleonitrile represented by the following formula (b) is known as a substance having a carbon double bond and a nitrile group in the structure. For example, a derivative is synthesized by reacting diaminomaleonitrile with another chemical substance, and the derivative may be a pharmaceutical, a dye, a pigment, a seasoning, a microbial culture agent, an agrochemical, an antibacterial agent, a polymer additive, or the like. Used as an intermediate material. Furthermore, diaminomaleonitrile is converted into a purine compound such as adenine, guanine, and xanthine through an imidazole compound, or is reacted with a sulfur compound or dialdehyde to contain an azole compound or a pyrazine compound. Nitrogen heterocyclic compounds can also be used, and these can be used as raw materials for pharmaceuticals, agricultural chemicals, pigments, dyes and the like.

On the other hand, an example in which a derivative is synthesized using only diaminomaleonitrile as a raw material has been reported. For example, Non-Patent Documents 1 and 2 disclose that a diaminomaleonitrile powder can be obtained by heat-treating diaminomaleonitrile powder at 197 to 997 ° C. for 1 hour in a nitrogen atmosphere. When the heat treatment temperature is 197 ° C., hydrazine is generated by thermal decomposition.
As another example of performing the same heat treatment, in Non-Patent Document 3, diaminomaleonitrile powder is sealed in an ampoule, or a catalytic amount of triethylamine is added to diaminomaleonitrile and sealed in an ampoule, and after decompression, It is disclosed that a heat-treated product of diaminomaleonitrile can be obtained by heat treatment at 125 ° C.

JP 2006-022137 A JP 2007-197672 A

Kenji Yamanaka et al., “Characteristics of Electric Double Layer Capacitor of Carbon / Nitrogen Material Prepared by Thermal Decomposition of DAMN”, Annual Meeting of Carbon Society of Japan, p. 190-191 (2005) Masayuki Kawaguchi et al., “Preparation of Carbon / Nitrogen Materials Using Diaminomaleonitrile and Electrochemical Capacitor Properties”, Annual Meeting of Carbon Society of Japan, p. 280-281 (2006) THE JOURNAL OF CHEMICAL PHYSICS, 130 (13), 134504 (2009) “HCN polymers charactrized by SSNMR: Solid state reaction of crystalline tetramer” (diminomicon)

However, the development of derivatives of diaminomaleonitrile is not yet sufficient, and there is a need for a technique that can be converted into more highly functional substances and materials.
From this point of view, the present inventors examined a polymer of diaminomaleonitrile, and thought that it would be useful if a polymer with a developed π-conjugated structure could be provided.
The present invention has been made in view of such circumstances, and is a diaminomaleonitrile polymer that is a novel nitrogen-containing polymer material, and is useful as an organic electronic material, and is a diaminomaleonitrile that has developed a π-conjugated structure by imine The object is to provide a polymer.

As a result of intensive studies to solve the above problems, the present inventor has (i) a predetermined solubility in formic acid, and (ii) a molar ratio of nitrogen atoms to carbon atoms (N / C) is predetermined. The present invention has found that a diaminomaleonitrile polymer having a predetermined peak in a laser Raman spectrum diagram having a numerical range and (iii) wave number 1000 to 2000 cm ⁻¹ can solve the above-mentioned problems of the prior art. It came to make.
That is, the present invention is as follows.

[1]
Diaminomaleonitrile polymer satisfying the following conditions (i) to (iii):
(I) solubility in formic acid (A) is less than 0.0001,
(Ii) The molar ratio of nitrogen atom to carbon atom (N / C) is 0.65 to 0.90,
(Iii) In the laser Raman spectrum diagram of wave number 1000 to 2000 cm ⁻¹ ,
Peak P1 between 1390~1425cm ^-1, has at least two main peaks of the peak P2 between 1500~1550cm ^-1,
And the ratio (L / H1) of the height L from the baseline of the minimum point M between P1 and P2 to the height H1 from the baseline of P1 is 0.70 to 0.95, The ratio of the height H2 from the baseline (L / H2) is 0.60 to 0.90.
[2]
A method for producing a diaminomaleonitrile polymer according to the above [1] ,
A method for producing a diaminomaleonitrile polymer comprising a step of polymerizing diaminomaleonitrile under a temperature condition of 201 ° C or higher in the presence of a solvent having a solubility of diaminomaleonitrile of 0.02 or higher.

  According to the present invention, it is possible to provide a diaminomaleonitrile polymer useful as an organic electronic material in which a π-conjugated structure by imine is developed.

The schematic diagram of an example of the laser Raman spectrum figure of the diaminomaleonitrile polymer in this embodiment is shown.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[Diaminomaleonitrile polymer]
The diaminomaleonitrile polymer of this embodiment is a diaminomaleonitrile polymer that satisfies the following conditions (i) to (iii).
(I) The solubility (A) in formic acid is less than 0.0001.
(Ii) The molar ratio of nitrogen atom to carbon atom (N / C) is 0.65 to 0.90.
(Iii) In the laser Raman spectrum diagram of wave number 1000 to 2000 cm ⁻¹ ,
Peak P1 between 1390～1425Cm ^-1, has at least two main peaks of the peak P2 between 1500～1550Cm ^-1, and high from baseline minimum point M between P1 and P2 The ratio of the height L to the height H1 from the baseline of P1 (L / H1) is 0.70 to 0.95, and the ratio of the height H2 from the baseline of P2 (L / H2) is 0. 60-0.90.

(Solubility in formic acid (A))
The diaminomaleonitrile polymer of this embodiment has a solubility (A) in formic acid of less than 0.0001, preferably 0.00005 or less, more preferably 0.00002 or less.
According to the study by the present inventors, a diaminomaleonitrile polymer obtained by polymerizing diaminomaleonitrile under a temperature condition of 80 to 200 ° C. in the presence of a solvent having a solubility of diaminomaleonitrile of 0.02 or more. Shows solubility in formic acid, and the solubility (A) is 0.01 to 0.05. When the polymerization temperature is lowered, the solubility (A) of the diaminomaleonitrile polymer in formic acid increases, and when the polymerization temperature is raised, the solubility (A) in formic acid tends to decrease.
Therefore, in the diaminomaleonitrile polymer of this embodiment, in order to control the solubility (A) in formic acid to less than 0.0001, it is effective to adjust the polymerization temperature to 201 ° C. or higher as described later. is there.

  The diaminomaleonitrile polymer of the present embodiment has a high molecular weight by adjusting the polymerization temperature to 201 ° C. or higher. Therefore, the solubility in formic acid is extremely low, and the π-conjugated structure by the imine conjugated structure is extremely developed. doing.

A method for measuring the solubility (A) in the formic acid of the diaminomaleonitrile polymer of this embodiment will be described.
1 g of diaminomaleonitrile polymer (prepared mass of diaminomaleonitrile polymer) and 100 g of formic acid (mass of solvent) were weighed and mixed, and stirred at 25 ° C. for 10 minutes. Suction filtration is performed using 5C (retained particle diameter: 1 μm (value described in catalog)), and the diaminomaleonitrile polymer remaining on the filter paper is recovered as a filtrate. The obtained filtrate is dried under reduced pressure at 120 ° C. for 10 hours, and the residual mass (g) of the diaminomaleonitrile polymer is measured.
The solubility (A) of the diaminomaleonitrile polymer in formic acid is defined by formula (I).
Solubility of diaminomaleonitrile polymer in formic acid (A)
= (Diaminomaleonitrile polymer charged mass-diaminomaleonitrile polymer residual mass) / formic acid mass = (1-diaminomaleonitrile polymer residual mass) / 100
... (I)

(Molar ratio of nitrogen atom to carbon atom (N / C))
The diaminomaleonitrile polymer of this embodiment has a molar ratio of nitrogen atoms to carbon atoms (hereinafter sometimes referred to as “N / C”) of 0.65 to 0.90, preferably 0.75. 0.87, more preferably 0.80 to 0.85. Thus, the diaminomaleonitrile polymer of the present embodiment is a polymer into which nitrogen atoms are introduced at a high rate.
N / C can be obtained by performing analysis using a CHN analyzer by a method in which oxygen and helium are circulated and burned. More specifically, it can be determined by the method described in Examples described later.
By setting N / C to 0.65 or more, a π-conjugated structure developed by imine can be obtained, and by setting it to 0.90 or less, an effect of reducing solubility in formic acid can be obtained.

Diaminomaleonitrile polymer of the present embodiment, in the laser Raman spectrum of the wave number 1000～2000Cm ^-1, a peak P1 between the wave number 1390～1425Cm ^-1, at least that the peak P2 between wavenumber 1500～1550Cm ^-1 Has two peaks. Preferably has a peak P1 between the wave number 1400～1420Cm ^-1, at least two main peaks of the peak P2 between wavenumber 1515~1525cm ^-1.
Peak P1 between wavenumbers 1390～1425Cm ^-1, a peak P2 between wavenumber 1500～1550Cm ^-1 are both C = N stretching vibration of the imine structure conjugation developed. Normally, C = N stretching vibrations such as imine are observed in the vicinity of a wave number of 1650 cm ⁻¹ , but it is known that when a conjugated structure is developed, it is significantly shifted to the lower wave number side. When at least two peaks are observed in the above range, it can be seen that there are at least two kinds of components having different imine conjugated chain lengths and structures around the C = N bond. In particular, the peak between wave numbers 1390 and 1425 cm ⁻¹ suggests the existence of a long imine conjugated structure.

In addition, the diaminomaleonitrile polymer of the present embodiment has a height L from the baseline at the minimum point M between the peaks P1 and P2 in the laser Raman spectrum diagram having a wave number of 1000 to 2000 cm ⁻¹ . The ratio of the height H1 from the baseline (L / H1) is 0.70 to 0.95, and the ratio of the height H2 from the baseline of P2 (L / H2) is 0.60 to 0.90. is there. Preferably, the ratio (L / H1) is 0.75 to 0.93 and the ratio (L / H2) is 0.70 to 0.85.

FIG. 1 shows a schematic diagram of an example of a laser Raman spectrum of the diaminomaleonitrile polymer of this embodiment. FIG. 1 is a diagram for explaining the ratio (L / H1) and the ratio (L / H2) used in this embodiment, and is a laser Raman obtained from the diaminomaleonitrile polymer in this embodiment. The spectrum diagram is not limited in any way.
As shown in FIG. 1, B1 is the minimum intensity value of 1000~1050cm ^-1, B2 is the minimum intensity value of 1850~2000cm ^-1. The base line in the laser Raman spectrum diagram used in the present embodiment is a straight line connecting B1 and B2.
C1 and C2 shown in FIG. 1 are intersections of a perpendicular line and a baseline drawn from the peaks P1 and P2 to the Raman shift axis, respectively.
The height H1 is the length from P1 to the intersection C1 of the perpendicular line and the baseline down to the Raman shift axis. Specifically, in the laser Raman spectrum diagram illustrated in FIG. 1, the length of the line segment P1-C1 It is. The height H2 is the length from P2 to the intersection C2 of the vertical line and the baseline drawn down to the Raman shift axis. Specifically, in the laser Raman spectrum diagram illustrated in FIG. 1, the length of the line segment P2-C2 It is.
D is the intersection of the perpendicular and the baseline drawn from the minimum intensity value M between the peaks P1 and P2 to the Raman shift axis.
The height L is the length from the above-mentioned M to the intersection D of the perpendicular line and the baseline drawn down to the Raman shift axis. Specifically, in the laser Raman spectrum diagram illustrated in FIG. 1, the length of the line segment MD is shown. That's it.

[Method for producing diaminomaleonitrile polymer]
The method for producing a diaminomaleonitrile polymer of this embodiment includes a step of polymerizing diaminomaleonitrile under a temperature condition of 201 ° C. or higher in the presence of a solvent having a solubility of diaminomaleonitrile of 0.02 or higher.

  As the polymerization monomer, diaminomaleonitrile may be a commercially available product, or may be produced based on a known method (for example, see JP-A-49-126619, JP-A-60-651158, etc.). May be. Diaminomaleonitrile may be purified by a method such as recrystallization to increase the purity, or may be unpurified. The diaminomaleonitrile thus obtained is usually a powder at normal temperature and pressure, and such a powder can also be used as a raw material.

As the solvent, a solvent having a solubility (x) of diaminomaleonitrile of 0.02 or more is used. Preferably it is 0.10 or more, More preferably, it is 0.25 or more.
When the solubility (x) of diaminomaleonitrile in the solvent is 0.02 or more, a sufficient reaction rate can be obtained when diaminomaleonitrile is polymerized in the liquid phase.
The upper limit of the solubility (x) of diaminomaleonitrile is preferably 1.00 or less.
A method for measuring the solubility (x) of diaminomaleonitrile in a solvent will be described.
10 g of diaminomaleonitrile (mass of diaminomaleonitrile) and 10 g of solvent (mass of solvent) were weighed and mixed, stirred at 25 ° C. for 10 minutes, and then manufactured by ADVANTEC, model no. Suction filtration is performed using a filter paper of 5C (retained particle diameter 1 μm (value described in the catalog)), and diaminomaleonitrile remaining on the filter paper is recovered as a filtrate. The obtained filtrate is dried under reduced pressure at 120 ° C. for 10 hours, and the residual mass (g) of diaminomaleonitrile is measured. The solubility (x) of diaminomaleonitrile in the solvent is defined by the formula (II).
Solubility of diaminomaleonitrile in solvent (x)
= (Diaminomaleonitrile charge mass-diaminomaleonitrile residual mass) / Solvent mass = (10-Diaminomaleonitrile residual mass) / 10
... (II)

As the solvent, one type of solution may be used alone, or two or more types of solutions may be used in combination.
When two or more kinds of solutions are used in combination, the mixture may be liquid and the solubility of diaminomaleonitrile may be 0.02 or more. Furthermore, a solid or gaseous substance is mixed with one or more liquid substances, and finally the mixture is liquid and the solubility of diaminomaleonitrile is 0.02 or more. If it is a thing, it can also be used as a solvent.

Examples of the liquid substance include, but are not limited to, water, alcohols (such as methanol, ethanol, propanol, and butanol), acetone, ethers (such as diethyl ether and tetrahydrofuran), and chlorinated carbonization. Hydrogens (dichloromethane, chloroform, dichloroethylene, trichloroethylene, carbon tetrachloride, etc.), glycols (ethylene glycol, propylene glycol, etc.), nitriles (acetonitrile, propionitrile, benzonitrile, etc.), amides (N, N-dimethyl) Formamide, dimethylacetamide, etc.), lactams (N-methyl-2-pyrrolidone, etc.), dimethyl sulfoxide, aliphatic hydrocarbons (n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, etc.), aroma Family carbonization Elements (benzene, toluene, xylene, ethylbenzene, etc.), ammonia, primary amines (methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecyl Amine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, cyclopropylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, catecholamine, phenethylamine, amantadine, toluidine, benzylamine, naphthylamine , Allylamine, etc.), secondary amine (dimethylamine, diethylamine, dipropylamine, dibutylamine) ), Tertiary amine (trimethylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, N-methylpyrrolidine, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) ), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), N, N-diisopropylethylamine, triethanolamine, etc.), quaternary amine (tetraethylammonium hydroxide, tetramethylammonium chloride, tetra) Methylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, etc.), cyclic amines (pyridine, 4-dimethylaminopyridine, pyrimidine, piperidine, morpholine, piperazine, quinuclide) , 1,4-diazabicyclo [2.2.2] octane, etc.), polyvalent amines (trimethylenediamine, ethylenediamine, diethylethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneexamine, tetramethylethylenediamine, diethylenetriamine, 1,2,3 At least selected from the group consisting of triaminopropane, triaminobenzene, triaminophenol, melamine, spermidine, 1,8-bis (dimethylamino) naphthalene, spermine, etc. Those containing the seeds, can be cited.
Among these, from the viewpoint of promoting polymerization reaction and solubility of diaminomaleonitrile, ammonia, acetonitrile, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,5-diazabicyclo [4] .3.0] Nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), a solvent containing any one selected from the group consisting of water and the like. preferable.

The solid substance that can be used in combination with the liquid substance is not limited to the following. For example, an alkali metal salt (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, hydroxide Cesium, francium hydroxide, sodium cyanide, sodium acetate, sodium carbonate, sodium bicarbonate, sodium borate, potassium cyanide, potassium acetate, potassium carbonate, potassium borate, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide ), Alkaline earth metal hydroxide (beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide, magnesium cyanide, magnesium acetate, magnesium carbonate, cyanide) Karshi , Calcium acetate, calcium carbonate, etc.), metal alkoxide (lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium tert-butoxide, lithium- tert-butoxide, aluminum tributoxide, etc.), organometallic compounds (diethyl magnesium, triethylaluminum, phenyllithium, etc.), Grignard reagents (phenylmagnesium bromide, ethylmagnesium chloride, allylmagnesium iodide, etc.), metal amide compounds (lithium amide, Potassium succinimide, potassium acetamido, etc.), oil-soluble azo compounds (2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), 2,2′- Azobis (2-methylbutyronitryl), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], [(cyano- 1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide, etc.), water-soluble azo system Compound (2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propaline ] Disulfate dihydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2 , 2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane), 2,2′-azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, azobiscyanovaleric acid, 2,2′-azobis {2-methyl-N- [1,1-bis (Hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propion , Etc.), peroxides (diisobutyryl peroxide, di-n-propyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, dilauroyl peroxide, 2,5 -Dimethyl-2,5-di (ethylhexanoylperoxy) hexane, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di (tert-butylperoxy) -2-methylcyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, tert-butylperoxymaleic acid, tert-hexylperoxybenzoate, etc.).
Among these, from the viewpoint of solubility of the solid component in the solvent, alkali metal salts such as potassium cyanide, metal alkoxides such as lithium-tert-butoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), etc. Oil-soluble azo compounds are preferred.

  Examples of gaseous substances that can be used in combination with the liquid substance include ammonia.

As above-mentioned, a solvent may be used individually by 1 type and may use 2 or more types together.
Examples of the mixed solvent containing two or more solvents include, but are not limited to, ammonia, acetonitrile, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1 , 5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), including two or more selected from the group consisting of water and the like. A mixed solvent is mentioned as a preferable solvent.
As a more preferable mixed solvent, for example, (a) one or more solvents selected from the group consisting of acetonitrile, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, water and the like (B) selected from the group consisting of ammonia, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and the like. And a mixed solvent containing one or more amines. By using (a) and (b) in combination, the solubility of diaminomaleonitrile in the solvent can be further improved.

The mass ratio (y) of the solvent to diaminomaleonitrile is preferably 0.5 to 10000, more preferably 0.7 to 100, still more preferably 0.8 to 10, and still more preferably 1. ~ 3.
Here, the mass ratio (y) is defined by the formula (III).
In addition, the mass of the solvent in Formula (III) is components other than diaminomaleonitrile used for superposition | polymerization, and the solid component mentioned above is also included.
Mass ratio of solvent to diaminomaleonitrile (y) = mass of solvent / mass of diaminomaleonitrile
... (III)

The polymerization reaction temperature in the polymerization step of the diaminomaleonitrile polymer is preferably 201 to 400 ° C., more preferably from the viewpoint of obtaining a high degree of polymerization, sufficiently increasing the molecular weight, and preventing decomposition and carbonization of the diaminomaleonitrile. Is 210-360 degreeC, More preferably, it is 240-320 degreeC, More preferably, it is 260-300 degreeC.
Moreover, N / C of a diaminomaleonitrile polymer can be controlled to 0.65-0.90 by superposing | polymerizing a diaminomaleonitrile within the said temperature range.

  Regarding the polymerization reaction pressure in the polymerization step of the diaminomaleonitrile polymer, when the polymerization operation is performed in a closed container and at a temperature equal to or higher than the boiling point of the solvent, the pressure is naturally increased. From the viewpoint of operability, it is preferably 0.10 to 10.0 MPa, more preferably 0.15 to 7.5 MPa, and further preferably 0.20 to 5.0 MPa.

  The polymerization reaction time in the polymerization step of the diaminomaleonitrile polymer is preferably 1 minute to 240 hours, more preferably 10 minutes to 100 hours, and even more preferably 30 minutes to 50 hours.

For the polymerization reaction, a batch reactor may be used, or a flow reactor may be used. The flow reactor may be a complete mixing tank, a tubular reactor, or a combination of a complete mixing tank and a tubular reactor.
The atmosphere in the reactor may be air, but is preferably an inert gas such as nitrogen, helium, or argon.

  In the production method of the present embodiment, since the diaminomaleonitrile polymer is precipitated as a solid in a solvent, steps such as separation, recovery, and purification can be easily performed. After the above polymerization reaction, it can be recovered by a liquid-solid separation method such as suction filtration. The recovered diaminomaleonitrile polymer can be washed and purified using acetonitrile or acetone. The purified diaminomaleonitrile polymer can be made into a powder form by removing the washing liquid by a method such as drying under reduced pressure.

  In the production method of the present embodiment, the reaction temperature may be changed in order to control the solubility (A) in the formic acid described above. For example, A tends to increase by lowering the reaction temperature, and A tends to decrease by raising the reaction temperature.

  In the production method of this embodiment, the reaction temperature may be changed in order to control the above N / C. For example, N / C tends to increase by lowering the reaction temperature, and N / C tends to decrease by increasing the reaction temperature.

  In the production method of the present embodiment, the reaction temperature may be changed in order to control the positions of P1 and P2 in the above-described laser Raman spectrum diagram. For example, when the reaction temperature is lowered, P1 and P2 tend to shift to the longer wavelength side, and when the reaction temperature is raised, P1 and P2 tend to shift to the lower wavelength side. Moreover, what is necessary is just to change reaction temperature in order to control L / H1 and L / H2 in an above-mentioned laser Raman spectrum figure. For example, L / H1 and L / H2 tend to increase by lowering the reaction temperature, and L / H1 and L / H2 tend to decrease by increasing the reaction temperature.

  Since the diaminomaleonitrile polymer of this embodiment can be used as a polymer material having the above-described π-conjugated structure, a conductive polymer material, an electric double layer capacitor, an organic EL element, an organic thin film transistor, a solar cell material In addition, it can be used as an organic electronic material useful as a member such as an antistatic material, a transparent conductive film, and a solid electrolytic capacitor.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these. Accordingly, those skilled in the art can implement the present invention by making various modifications to the examples described below.

The measurement methods applied in the examples and comparative examples will be described below.
(Measurement of solubility (A) of diaminomaleonitrile polymer in formic acid)
1 g of diaminomaleonitrile polymer (prepared mass of diaminomaleonitrile polymer) and 100 g of formic acid (mass of formic acid) were weighed and mixed, and stirred at 25 ° C. for 10 minutes. Suction filtration was performed using a filter paper of 5C (retained particle diameter 1 μm (value described in the catalog)), and the diaminomaleonitrile polymer remaining on the filter paper was recovered as a filtrate.
The obtained filtrate was dried under reduced pressure at 120 ° C. for 10 hours, and the residual mass (g) of the diaminomaleonitrile polymer was measured.
The solubility (A) of the diaminomaleonitrile polymer in formic acid was calculated based on the formula (I).
Solubility of diaminomaleonitrile polymer in formic acid (A)
= (Diaminomaleonitrile polymer charged mass-diaminomaleonitrile polymer residual mass) / formic acid mass = (1-diaminomaleonitrile polymer residual mass) / 100
... (I)

(CHN analysis)
N / C was calculated by measuring the atomic ratio of carbon, hydrogen, and nitrogen in the diaminomaleonitrile polymer.
Using a MICRO CORDER JM10 manufactured by Jess Lab Co., Ltd., a sample of 2500 μg was filled in a sample stage and subjected to CHN analysis.
The sample furnace was set to 950 ° C., the combustion furnace (copper oxide catalyst) was set to 850 ° C., and the reduction furnace (consisting of a silver grain + copper oxide zone, a reduced copper zone, and a copper oxide zone) was set to 550 ° C.
Oxygen was set to 15 mL / min, and He was set to 150 mL / min.
As the detector, a thermal conductivity detector (TCD) was used.
Calibration was performed by the method described in the manual using Antipyrine.

(Laser Raman spectrum measurement)
In the laser Raman spectrum measurement, the sample was pulverized with an agate mortar, mounted on a powder cell, and measured under the following conditions.
Apparatus: NRS-3200 manufactured by JASCO Corporation, light source: Ar laser (wavelength 532 nm, 2 mW), beam size 5 μm, objective lens 100x, operation range 1000 to 2000 cm ⁻¹ , exposure time 50 seconds, integration number 4 times.
In the obtained laser Raman spectral diagram, the peak (P1) between the 1390～1425Cm ^-1, were observed a peak (P2) between the 1500~1550cm ^-1.
Next, the ratio (L / H1) of the height L from the baseline of the minimum point M between the P1 and P2 to the height H1 from the baseline of P1, and the height from the baseline of P2 The ratio of thickness H2 (L / H2) was calculated.

(Measurement of solubility of diaminomaleonitrile in solvent)
10 g of diaminomaleonitrile (mass of diaminomaleonitrile) and 10 g of solvent (mass of solvent) were weighed and mixed, stirred at 25 ° C. for 10 minutes, and then manufactured by ADVANTEC, model no. Suction filtration was performed using a filter paper of 5C (retained particle diameter 1 μm (value described in the catalog)), and diaminomaleonitrile remaining on the filter paper was recovered as a filtrate.
The obtained filtrate was dried under reduced pressure at 120 ° C. for 10 hours, and the residual mass (g) of diaminomaleonitrile was measured.
The solubility (x) of diaminomaleonitrile in the solvent was calculated based on the formula (II).
Solubility of diaminomaleonitrile in solvent (x)
= (Diaminomaleonitrile charge mass-diaminomaleonitrile residual mass) / Solvent mass = (10-Diaminomaleonitrile residual mass) / 10
... (II)

(Measurement of mass ratio of solvent to diaminomaleonitrile)
The mass ratio (y) of the solvent to diaminomaleonitrile was calculated by the formula (III).
Mass ratio of solvent to diaminomaleonitrile (y) = mass of solvent / mass of diaminomaleonitrile (III)

[Example 1]
N, N-dimethylformamide (DMF) 100.0 g and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) 3.6 g were mixed to obtain a mixed solution, which was used as a solvent.
The solubility (x) of diaminomaleonitrile (N / C = 1) in this solvent was 0.95.
The polymerization reaction was carried out in a closed separable reactor manufactured by SUS316.
The closed reactor was equipped with stirring blades, and the system was always stirred by connecting to a stirrer.
The lower part of the reactor was charged with 103.6 g of the solvent and 80.0 g of diaminomaleonitrile powder and mixed.
That is, the mass ratio (y) of the solvent to diaminomaleonitrile was set to 1.30.
After fixing the upper part of the reactor to the lower part of the reactor with a clamp, the lower part of the reactor was fixed in a mantle heater.
The reactor was purged with nitrogen. The temperature of the mantle heater was set to 210 ° C. and maintained at 210 ° C. for 5 hours, then the mantle heater was removed, the reactor was naturally cooled, the top of the reactor was removed, and the diaminomaleonitrile polymer was manufactured by ADVANTEC, : No. The sample was collected by suction filtration using 5C (retained particle diameter 1 μm (catalog value)) filter paper.
The recovered crude diaminomaleonitrile polymer is washed with the solvent used, then washed with acetonitrile and acetone, and dried under reduced pressure at 120 ° C. for 10 hours in a vacuum dryer to recover 71.9 g of diaminomaleonitrile polymer. did. The yield was 89.9%.
The solubility (A) of the obtained diaminomaleonitrile polymer in formic acid was 0.00009. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.83. The results of laser Raman spectrum measurement are shown in Table 1 below.

[Example 2]
N, N-dimethylformamide (DMF) 100.0 g and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) 3.6 g were mixed to obtain a mixed solution, which was used as a solvent.
The solubility (x) of diaminomaleonitrile (N / C = 1) in this solvent was 0.95.
The polymerization reaction was carried out under the same conditions as in Example 1 except that the reaction temperature in Example 1 was changed to 260 ° C.
In addition, the said solvent 103.6g and diaminomaleonitrile powder 80.0g were used, and mass ratio (y) of the solvent with respect to diaminomaleonitrile was set to 1.30.
After completion of the polymerization reaction, 71.0 g of diaminomaleonitrile polymer was recovered. The yield of the polymerization reaction was 88.7%.
The solubility (A) of the resulting diaminomaleonitrile polymer in formic acid was 0.00005. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.81. The results of laser Raman spectrum measurement are shown in Table 1 below.

Example 3
N, N-dimethylformamide (DMF) 100.0 g and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) 3.6 g were mixed to obtain a mixed solution, which was used as a solvent.
The solubility (x) of diaminomaleonitrile (N / C = 1) in this solvent was 0.95.
The polymerization reaction was carried out under the same conditions as in Example 1 except that the reaction temperature in Example 1 was changed to 320 ° C.
In addition, the said solvent 103.6g and diaminomaleonitrile powder 80.0g were used, and mass ratio (y) of the solvent with respect to diaminomaleonitrile was set to 1.30.
After completion of the polymerization reaction, 70.0 g of diaminomaleonitrile polymer was recovered. The yield of the polymerization reaction was 87.5%.
The solubility (A) of the obtained diaminomaleonitrile polymer in formic acid was 0.00002. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.79. The results of laser Raman spectrum measurement are shown in Table 1 below.

Example 4
100.0 g of dimethyl sulfoxide (DMSO), 1.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (ADBN) were mixed and mixed to obtain a mixed solution, which was used as a solvent.
The solubility (x) of diaminomaleonitrile (N / C = 1) in this solvent was 0.85.
The polymerization reaction was carried out under the same conditions as in Example 1 except that the solvent used in Example 1 was changed to the above solvent and the reaction conditions were 210 ° C.
In addition, 101.8 g of the solvent and 80 g of diaminomaleonitrile powder were used, and the mass ratio (y) of the solvent to diaminomaleonitrile was set to 1.27.
After the completion of the polymerization reaction, 73.4 g of diaminomaleonitrile polymer was recovered. The yield of the polymerization reaction was 91.7%.
The solubility (A) of the obtained diaminomaleonitrile polymer in formic acid was 0.00009. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.86. The results of laser Raman spectrum measurement are shown in Table 1 below.

Example 5
100.0 g of N-methyl-2-pyrrolidone (NMP) was used as a solvent.
The solubility (x) of diaminomaleonitrile (N / C = 1) in this solvent was 0.75.
The polymerization reaction was performed under the same conditions as in Example 1 except that the solvent used in Example 1 was changed to the above solvent and the reaction temperature was 260 ° C.
In addition, 100 g of the solvent and 80 g of diaminomaleonitrile powder were used, and the mass ratio (y) of the solvent to diaminomaleonitrile was set to 1.25.
After completion of the polymerization reaction, 72.4 g of diaminomaleonitrile polymer was recovered. The yield of the polymerization reaction was 90.5%.
The solubility (A) of the obtained diaminomaleonitrile polymer in formic acid was 0.00006. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.84. The results of laser Raman spectrum measurement are shown in Table 1 below.

[Comparative Example 1]
The polymerization reaction was carried out under the same conditions as in Example 1 except that no solvent was used and the reaction conditions were 397 ° C. and 1 hour.
That is, only 80.0 g of diaminomaleonitrile (N / C = 1) powder was charged into the reactor to carry out the polymerization reaction.
After completion of the polymerization reaction, about 28.0 g of black powder was recovered from the reactor.
The yield of the polymerization reaction was 35.0%.
The solubility (A) of the resulting diaminomaleonitrile polymer in formic acid was 0.00001. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.51. The results of laser Raman spectrum measurement are shown in Table 1 below.

[Comparative Example 2]
The polymerization reaction was carried out under the same conditions as in Example 1 except that the solvent was not used, the reaction conditions were 125 ° C., 12 hours, and the reactor was evacuated and depressurized before the reaction.
That is, only 80.0 g of diaminomaleonitrile (N / C = 1) powder was charged into the reactor to carry out the polymerization reaction.
After the completion of the polymerization reaction, 74.7 g of a blackish brown powder was recovered from the reactor, most of which was dissolved in dimethyl sulfoxide (DMSO).
Those dissolved were judged to be unreacted diaminomaleonitrile or oligomers having a low polymerization degree. Therefore, about 1.2 g of black powder that was not dissolved in dimethyl sulfoxide was recovered as a diaminomaleonitrile polymer.
The yield was 1.5%.
The solubility (A) of the resulting diaminomaleonitrile polymer in formic acid was 0.02500. N / C of the diaminomaleonitrile polymer by CHN analysis was 0.95. The results of laser Raman spectrum measurement are shown in Table 1 below.

  Table 1 shows the polymerization reaction conditions and the physical properties of the polymers in Examples 1 to 5 and Comparative Examples 1 and 2.

x: Solubility of solvent diaminomaleonitrile y: Mass ratio of solvent to diaminomaleonitrile A: Solubility of diaminomaleonitrile polymer in formic acid N / C: N / C of diaminomaleonitrile polymer by CHN analysis
P1: peaks between 1390~1425cm ^-1 P2: peaks between 1500~1550cm ^-1 L: P1 and height from the baseline of the minimum point M between P2 H1: height from baseline P1 H2: Height from baseline of P2

  The diaminomaleonitrile polymer according to the present invention is used as an organic electronic material such as a conductive polymer material, an electric double layer capacitor, an organic EL element, an organic thin film transistor, a solar cell material, an antistatic material, a transparent conductive film, and a solid electrolytic capacitor. it can.

Claims (2)

A diaminomaleonitrile polymer satisfying the following conditions (I) to (III):
(I) solubility in formic acid (A) is less than 0.0001,
(II) The molar ratio of nitrogen atom to carbon atom (N / C) is 0.65 to 0.90,
(III) In the laser Raman spectrum diagram of wave number 1000 to 2000 cm ⁻¹ ,
Peak P1 between 1390~1425cm ^-1, has at least two main peaks of the peak P2 between 1500~1550cm ^-1,
And the ratio (L / H1) of the height L from the baseline of the minimum point M between P1 and P2 to the height H1 from the baseline of P1 is 0.70 to 0.95, The ratio of the height H2 from the baseline (L / H2) is 0.60 to 0.90. A method for producing a diaminomaleonitrile polymer according to claim 1 , comprising:
A method for producing a diaminomaleonitrile polymer comprising a step of polymerizing diaminomaleonitrile under a temperature condition of 201 ° C or higher in the presence of a solvent having a solubility of diaminomaleonitrile of 0.02 or higher.