JP2014156381A - Hydrocyanic acid polymer and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safe and efficient method of manufacturing a hydrocyanic acid polymer, capable of providing a hydrocyanic acid polymer having a relatively high molecular weight, large absorption intensity in a long-wavelength side of an ultraviolet visible absorption spectrum and an efficiently developed conjugated structure, and to provide a hydrocyanic acid polymer having the aforementioned physical properties.SOLUTION: There is provided a hydrocyanic acid polymer having 0.10 or more of absorption intensity of light having a wavelength of 600 nm in an ultraviolet visible absorption spectrum of a 0.01 mass% formic acid solution.

Description

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

  It is known that a cyanide polymer is useful as a precursor of a novel nitrogen-containing carbon material because of its high nitrogen content in its structure. Nitrogen-containing carbon materials are considered promising for use as electrode material as redox catalysts for lithium ion secondary battery negative electrodes, capacitor electrodes, and fuel cell electrodes, for example. Patent Document 1 describes a method for producing a nitrogen-containing carbon material for an oxidation-reduction catalyst for a fuel cell electrode by performing an activation treatment on a cyanate polymer with an inert gas.

  The cyanide polymer can be produced by polymerizing cyanide by various methods. Non-Patent Document 1 discloses a method for obtaining a hydrocyanic acid polymer, a method of heating liquid hydrocyanic acid or a hydrocyanic acid aqueous solution, a method of leaving hydrocyanic acid for a long time, a method of adding a base to hydrocyanic acid, a method of irradiating hydrocyanic acid with light, hydrocyanic acid A method of performing various discharges or a method of electrolyzing an aqueous potassium cyanide solution is disclosed.

Non-Patent Document 1 discloses a method of adding a base to hydrocyanic acid, specifically, a method of adding ammonia water to hydrocyanic acid to obtain a hydrocyanic acid polymer. Although there are various theories regarding the structure of the cyanide polymer, Non-Patent Document 1 does not retain the prototype of the cyanate structure, and has a π-conjugated structure with a carbon-nitrogen double bond in a planar double ladder structure with a six-membered ring. A cyanide polymer having a structure represented by the following formula (1) has been proposed.
(In the formula, m is an arbitrary number.)

Non-Patent Document 2 discloses a method of synthesizing a hydrocyanic acid polymer at room temperature by contacting ammonia gas directly with hydrocyanic acid without using a solvent. It has been disclosed that the obtained polymer exhibits a property of being dissolved in dimethyl sulfoxide. From the result of structural analysis by solution nuclear magnetic resonance method, a cyanide polymer having a structure represented by the following formula (2) has been proposed. ing.
(In the formula, m is an arbitrary number.)

  Furthermore, Non-Patent Document 3 discloses a method for producing a cyanide polymer by adding a base such as triethylamine to liquid hydrocyanic acid. It is disclosed that the polymer obtained by the method described in Non-Patent Document 3 contains a polymer having a low molecular weight. Furthermore, it discloses that a component having a low molecular weight exhibits a property of being dissolved in dimethyl sulfoxide, while there is a component that is not soluble in a general organic solvent.

  On the other hand, in Non-Patent Document 4, since hydrocyanic acid has an unstable property, in the process of producing a hydrocyanic acid polymer, particularly when hydrocyanic acid contains a trace amount of impurities such as water, a storage container for explosive progression of the polymerization reaction It is disclosed that there is a risk of an increase in internal pressure, sudden heat generation, and sometimes explosion.

WO2007 / 043311

TH. Voelker, “Polymere Brausauere”, Angelwante Chemie, 72, 379-384 (1960) Chao He, et. al, "Structural Investigation of HCN Polymer Isotopomers by Solution-State Multidimensional NMR," The Journal of Physical Chemistry A, 11620, 51, 2047. Masahiro Kurabayashi, Yasunobu Yanagiya, Masahiko Yasumoto, Takuro Kamakura, “Polymerization Products of Hydrogen Cyanide with Alkali”, Industrial Science Journal, 70, 7, 1106-1111 (1967) Kurabayashi Masahiro, Yanagiya Yasumoto, Yasumoto Masahiko, “Danger and Effect of Water by Polymerization of Liquid Hydrogen Cyanide”, Industrial Science Journal, Vol. 71, No. 8, 1119-1123 (1968)

  Cyanic acid polymer is promising as a precursor of a novel nitrogen-containing carbon material. On the other hand, the cyanide polymer obtained by the conventional production method is a polymer containing a large amount of a polymer having a low molecular weight or a polymer having a low molecular weight. Thus, the conventional cyanide polymer having a low molecular weight has a weak absorption intensity on the long wavelength side of the ultraviolet-visible absorption spectrum, and the π-conjugated system is not sufficiently developed. The cyanide polymer is considered to develop a π-conjugated system as the molecular weight increases, and accordingly, electrochemical properties such as conductivity are developed. It can be expected that the cyanide polymer itself can be used as a polymer material due to the development of electrochemical characteristics. However, the conventional method for producing a hydrocyanic acid polymer has a problem in terms of the molecular weight and purity of the obtained hydrocyanic acid polymer. In addition, the method for producing a hydrocyanic acid polymer has not been sufficiently established from the viewpoint of safety due to the instability of hydrocyanic acid, and there is room for improvement.

  The present invention has been made in view of the above problems, and can obtain a hydrocyanic acid polymer having a relatively high molecular weight, a large absorption wavelength on the long wavelength side of an ultraviolet-visible absorption spectrum, and a sufficiently conjugated structure developed. An object of the present invention is to provide a safe and highly efficient process for producing a cyanate polymer and a cyanate polymer having the above-mentioned physical properties.

  As a result of intensive research in order to solve the above problems, the present inventor has surprisingly been able to safely and highly efficiently perform cyanide polymerization by adding a base to acid-stabilized cyanate and polymerizing it. It was found that the product can be produced, and the obtained cyanate polymer has a relatively high molecular weight, the absorption wavelength on the long wavelength side of the UV-visible absorption spectrum is large, and the conjugated structure is sufficiently developed. The present invention has been completed.

That is, the present invention is as follows.
[1]
A cyanide polymer having an absorption intensity of light having a wavelength of 600 nm of 0.10 or more in an ultraviolet-visible absorption spectrum of a 0.01% by mass formic acid solution.
[2]
The cyanate polymer according to [1], wherein the weight average molecular weight is 5,000 or more.
[3]
The cyanide polymer according to [1] or [2] above, wherein the molar ratio of nitrogen atom to carbon atom (N / C) is 0.8 to 1.0.
[4]
The step 1 and the step include the step 1 of mixing an acid and a hydrocyanic acid to obtain a hydrocyanic acid containing an acid, and the step 2 of mixing a hydrocyanic acid and a base containing the acid to obtain a hydrocyanic acid polymer. 2 wherein the number of moles of the acid is a, the number of moles of the hydrocyanic acid is b, and the number of moles of the base is c, the x value of the following formula (I) satisfies 1 to 20: [1] to [3] a process for producing a cyanide polymer.
x = c / (a + 0.01 × b) (I)

  According to the present invention, safe and highly efficient hydrocyanic acid polymerization having a relatively high molecular weight, a large absorption wavelength on the long wavelength side of an ultraviolet-visible absorption spectrum, and a conjugated structure sufficiently developed can be obtained. The manufacturing method of a thing, and the cyanide polymer which has said physical property can be provided.

It is a graph which shows the ultraviolet visible absorption spectrum of the cyanuric acid polymer obtained in Example 1 and Comparative Example 2. It is a graph which shows the ultraviolet visible absorption spectrum of the cyanide polymer obtained in Example 15 and Comparative Example 2. It is a graph which shows the relationship between x value in a formula (I), and a cyanuric acid polymer yield.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited only to the embodiment. That is, the present invention can be variously modified without departing from the gist thereof.

[Polyuric acid polymer]
(UV-visible absorption spectrum)
In the ultraviolet-visible absorption spectrum of the formic acid solution containing 0.01% by mass of the cyanic acid polymer, the cyanic acid polymer according to this embodiment has an absorption intensity of light having a wavelength of 600 nm of 0.10 or more, preferably 0.12. It is above, More preferably, it is 0.15 or more. In addition, the upper limit of the absorption intensity of light having a wavelength of 600 nm is not particularly limited, and is preferably as high as possible. The cyanide polymer of this embodiment has strong absorption on the long wavelength side in this way, which means that it has a sufficiently developed π-conjugated structure, and has a structure desirable as an organic electronic material. It can be said that it is a polymer. Such a hydrocyanic acid polymer can be obtained by the method for producing a hydrocyanic acid polymer. By increasing the degree of polymerization of the cyanate polymer and developing a π-conjugated structure, the absorption intensity of light having a wavelength of 600 nm can be controlled to be higher. The absorption intensity of light having a wavelength of 600 nm can be measured by the method described in the examples.

(Weight average molecular weight)
The cyanate polymer of this embodiment is preferably a polymer having a high degree of polymerization. From this viewpoint, the weight average molecular weight of the cyanate polymer of this embodiment is preferably 5,000 or more, more preferably 7,500 or more, and further preferably 10,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 100,000 or less, more preferably 75,000 or less, and further preferably 50,000 or less. In addition, a weight average molecular weight can be calculated | required by the method as described in the Example mentioned later.

(Molar ratio of nitrogen atom to carbon atom)
In the cyanate polymer of the present embodiment, the molar ratio of nitrogen atoms to carbon atoms (hereinafter sometimes referred to as “N / C”) is preferably 0.8 to 1.0, more preferably 0.8. It is 85-1.0, More preferably, it is 0.9-1.0. Thus, the cyanate polymer of this embodiment can be a polymer in which nitrogen atoms are introduced at a high rate. When the reaction temperature is lowered, N / C tends to increase, and when the reaction temperature is raised, N / C tends to decrease. N / C also changes depending on the amount and type of base used for polymerization. As the amount of base increases, the value of N / C tends to decrease. The influence of the type of base is difficult to describe in general, but when a bulky organic amine is used, N / C tends to be small. In addition, N / C can be calculated | required with an organic trace element analyzer (The product made from a J Science lab company, MICRO CORDER JM10).

[Production method of cyanide polymer]
The method for producing a cyanate polymer according to this embodiment is as follows.
Step 1 of mixing acid and hydrocyanic acid to obtain hydrocyanic acid containing acid;
A step 2 of mixing an acid-containing hydrocyanic acid and a base to obtain a hydrocyanic acid polymer,
In Step 1 and Step 2, when the number of moles of acid is a, the number of moles of hydrocyanic acid is b, and the number of moles of the base is c, the x value of the following formula (I) satisfies 1 or more and 20 or less.
x = c / (a + 0.01 × b) (I)

[Step 1]
Step 1 of this embodiment is a step of mixing acid and hydrocyanic acid to obtain hydrocyanic acid containing acid. The method of mixing hydrocyanic acid and acid is not particularly limited, and acid may be added to hydrocyanic acid, or hydrocyanic acid may be added to the acid. In either case, the acid can be a cyanuric acid. Here, the “acid” mixed with hydrocyanic acid refers to an acid other than hydrocyanic acid contained in hydrocyanic acid.

(Purocyanic acid and its production method)
The hydrocyanic acid used for producing the hydrocyanic acid polymer is not particularly limited, and those produced by a known method can be used. For example, in the method of producing acrylonitrile or methacrylonitrile by a gas phase catalytic reaction in which propylene, isobutylene, tert-butyl alcohol, propane, or isobutane is reacted with ammonia or an oxygen-containing gas in the presence of a catalyst, byproduct cyanide is produced. Can be used. At this time, a raw material that generates hydrocyanic acid by an ammoxidation reaction, such as methanol, may be supplied to the reactor. Further, it may be a laboratory manufacturing method using a soda blue soda or the like.

(acid)
Acids other than cyanic acid to be mixed with cyanic acid are not particularly limited. For example, hyponitrous acid, nitrous acid, nitric acid, fuming nitric acid, sulfurous acid, sulfuric acid, peroxomonosulfuric acid, peroxodisulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfamine Acid, fluorosulfonic acid, hydrochloric acid, carbonic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, phosphorous acid, phosphoric acid, next Iodic acid, iodic acid, periodic acid, hypofluoric acid, hydrofluoric acid, boric acid, chromic acid, dichromic acid, arsenous acid, arsenic acid, selenious acid, selenic acid, xenonic acid, perxenone Inorganic acids such as acids; lactic acid, citric acid, acetic acid, formic acid, succinic acid, sulfinic acid, tycoic acid, phosphonic acid, benzoic acid, 2-iodoxybenzoic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, perfluorooctane Sulfonic acid, indole-3-acetic acid, 4-chloroindole-3-acetic acid, acrylic acid, aconitic acid, maleic acid, fumaric acid, sialic acid, aristolochic acid, N-acetylneuraminic acid, acetoacetic acid, abietic acid, Abscisic acid, aminolevulinic acid, angelic acid, butyric acid, isobutyric acid, propionic acid, imidazol-4-one-5-propionic acid, urocanic acid, ethylenediaminetetraacetic acid (edetic acid), glycol etherdiaminetetraacetic acid, okadaic acid, succinic acid , Oxalosuccinic acid, 3-hydroxybenzoic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, isocitric acid, carcinine, citric acid, glycolic acid, glyceric acid, salicylic acid, shikimic acid, tartaric acid, 4-hydroxybenzoic acid, 3 -Hydroxyisobutyric acid, hydroxycitric acid 3-hydroxybutyric acid, hydroxybutyric acid, 2-hydroxybutyric acid, prefenic acid, mandelic acid, mevalonic acid, monohydroxybenzoic acid, malic acid, 10-camphorsulfonic acid, cysteic acid, dinonylnaphthylsulfonic acid, diiodomethylparastryl Examples of the organic acid include sulfone, taurine, trifluoromethanesulfonate, trifluoromethanesulfonate, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and methanesulfonic acid. These acids have an effect of stabilizing hydrocyanic acid by being contained in hydrocyanic acid or a solution thereof, among which acetic acid and sulfuric acid are particularly preferable. Use of acetic acid and sulfuric acid tends to improve safety over a long period of time. The above acids may be used alone or in combination of two or more.

  The amount of acid mixed with hydrocyanic acid is preferably 0.1 to 60% by mass. When the amount of acid is in the above range, hydrocyanic acid can be further stabilized, and the safety tends to be superior. The amount of acid is more preferably 0.5 to 15% by mass, and further preferably 1 to 10% by mass. When the amount of the acid is within the above range, the heat of neutralization of the acid and the base that can be generated in Step 2 tends to be further suppressed.

  The acid-containing hydrocyanic acid may be used without a solvent, but is preferably mixed with a solvent and used as a solution. Examples of such a solvent include, but are not limited to, water; alcohols such as methanol, ethanol, propanol and butanol; acetone; ethers such as diethyl ether and tetrahydrofuran; dichloromethane, chloroform, dichloroethylene, trichloroethylene and carbon tetrachloride. Chlorinated hydrocarbons such as ethylene glycol, propylene glycol and the like; nitriles such as acetonitrile, propionitrile and benzonitrile; amides such as N, N-dimethylformamide and dimethylacetamide; N-methyl-2 -Lactams such as pyrrolidone; dimethyl sulfoxide; aliphatic hydrocarbons such as n-pentane, n-hexane, cyclohexane, n-heptane, n-octane; benzene, toluene, xylene, ethylben Aromatic hydrocarbons such as emissions and the like. Among these, water, acetonitrile, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like are more preferable. The said solvent may be used individually by 1 type, or may be used together 2 or more types.

  The concentration of hydrocyanic acid in the hydrocyanic acid solution containing acid is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, still more preferably 15 to 60% by mass, and even more preferably 25 to 50% by mass. It is. When the hydrocyanic acid concentration is 1% by mass or more, the polymerization rate tends to be faster. On the other hand, when the hydrocyanic acid concentration is 99% by mass or less, the generation of rapid polymerization heat tends to be further suppressed.

[Step 2]
Step 2 of the present embodiment is a step of mixing a hydrocyanic acid containing an acid and a base to obtain a hydrocyanic acid polymer. The method of mixing the acid-containing hydrocyanic acid solution and the base is not particularly limited, and the base may be mixed into the hydrocyanic acid solution containing the acid, or the hydrocyanic acid solution containing the acid may be mixed into the base. . A method in which a base is mixed with an acid-containing hydrocyanic acid solution is preferred.

(base)
The base capable of polymerizing the acid-containing hydrocyanic acid is not particularly limited. For example, ammonia water; methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine , Undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, catecholamine, phenethylamine, amantadine, toluidine, benzylamine, naphthylamine, Primary amines such as allylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine; Tylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, N-methylpyrrolidine, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] ] Tertiary amines such as undecene-7 (DBU), N, N-diisopropylethylamine, triethanolamine; tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, etc. Quaternary amines; cyclic amines such as pyridine, 4-dimethylaminopyridine, pyrimidine, piperidine, morpholine, piperazine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane Trimethylenediamine, ethylenediamine, diethylethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, phenylenediamine , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, diethylenetriamine, 1,2,3-triaminopropane, triaminobenzene, triaminophenol, melamine, spermidine, 1,8-bis ( Polymethylamines such as dimethylamino) naphthalene and spermine; lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, hydroxide Francium, 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, francium oxide, etc. Alkali metal salts of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide, magnesium cyanide, magnesium acetate, magnesium carbonate, calcium cyanide, calcium acetate, calcium carbonate, etc. Alkaline earth metal hydroxide: lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, sodium isopropyl Metal alkoxides such as xoxide, potassium-tert-butoxide, lithium-tert-butoxide, aluminum tributoxide; organometallic compounds such as diethylmagnesium, triethylaluminum, phenyllithium; phenylmagnesium bromide, ethylmagnesium chloride, allylmagnesium iodide, etc. Grignard reagents; metal amide compounds such as lithium amide, potassium succinimide, and acetamide potassium can be exemplified. The above bases may be used alone or in combination of two or more.

  Among these, ammonia water; diethylamine, triethylamine, tripropylamine, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 ( DBU) and the like; alkali metal salts such as potassium cyanide; metal alkoxides such as lithium tert-butoxide and the like are preferable. By using such a base, the polymerization reaction is more easily promoted, the handling is easier, and the purifying process of the cyanate polymer tends to be simpler.

  Cyanic acid may be copolymerized with other monomers. Examples of other monomers include, but are not limited to, acrylonitrile, ethylene, propylene, butadiene, styrene, methyl methacrylate, diaminomaleonitrile, and the like. When copolymerizing hydrocyanic acid with other monomers, the other monomers may be mixed in a hydrocyanic acid solution containing acid, or after mixing other monomers and hydrocyanic acid, the acid is added and the solvent or catalyst is added. Furthermore, you may mix. That is, the timing of adding each component and solvent is not limited.

  Although polymerization reaction temperature is not specifically limited, Preferably it is 10-200 degreeC, More preferably, it is 30-150 degreeC, More preferably, it is 50-120 degreeC, More preferably, it is 80-100 degreeC. When the polymerization reaction temperature is high, the molecular weight of the resulting polymer tends to increase, but N / C tends to decrease. When the polymerization reaction temperature is within the above range, a polymer having a high molecular weight and a high N / C can be obtained.

  The polymerization reaction pressure is not particularly limited, but is preferably 0.05 to 2.0 MPa, more preferably 0.08 to 1.5 MPa, and still more preferably 0.1 to 1.0 MPa. When the polymerization reaction pressure is in the above range, the reaction rate becomes faster and the safety tends to be further improved.

  The polymerization reaction time is not particularly limited, but is preferably 1 minute to 240 hours, preferably 10 minutes to 100 hours, and more preferably 30 minutes to 50 hours. When the polymerization reaction time is in the above range, the reaction rate becomes faster and the safety tends to be further improved.

  The polymerization reaction in step 2 may be performed using a batch reactor or a flow reactor. 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 may be an inert gas such as nitrogen, helium, or argon.

(Mixing ratio)
In Step 1 and Step 2, when the number of moles of acid is a, the number of moles of hydrocyanic acid is b, and the number of moles of the base is c, the x value of the following formula (I) satisfies 1 or more and 20 or less. The upper limit of x is preferably 10 or less, and more preferably 7 or less. Further, the lower limit of x is preferably 2 or more, and more preferably 3 or more. When the x value is in the above range, the polymerization reaction becomes more efficient and the yield becomes higher.
x = c / (a + 0.01 × b) (I)

The number of moles a of acid in formula (I) is defined as in formula (II). Here, the “valence” refers to the number of protons that one molecule can release. For example, 1 for acetic acid, nitric acid, and hydrochloric acid, 2 for sulfuric acid, and 3 for phosphoric acid.
a (mol) = mass of acid (g) ÷ molecular weight of acid × valence (II)

The number of moles c of the base in formula (I) is defined as in formula (III). Here, the “valence” means the number of hydroxyl groups in one molecule in the case of a Bronsted base, and the number of protons that can be accepted by one molecule in the case of an Arrhenius base. For example, 1 for sodium hydroxide, ammonia, diethylamine and triethylamine, 2 for ethylenediamine and diethylethylenediamine, and 3 for diethylenetriamine.
c (mol) = base mass (g) ÷ base molecular weight × valence (III)

[Separation, recovery and purification processes]
In the method for producing a cyanide polymer according to this embodiment, after the above-described polymerization reaction, the cyanide polymer is precipitated as a solid in a solvent, so that the steps of separation, recovery, and purification are relatively easy. The cyanate polymer precipitated as a solid can be recovered by a liquid-solid separation method such as suction filtration. The recovered cyanic acid polymer can be washed and purified using water, acetonitrile, acetone or the like. The purified cyanate polymer can be made into a powder form by removing the washing solution by a method such as drying under reduced pressure.

  Since the cyanide polymer of this embodiment has a high nitrogen content, it can be used as a precursor of a nitrogen-containing carbon material. Nitrogen-containing carbon materials are useful for electrode material applications such as lithium ion secondary batteries, capacitors, and fuel cells.

  Since the cyanate polymer of the present embodiment has the above-described π-conjugated structure, it can also be used as a polymer material. Therefore, a conductive polymer material, an electric double layer capacitor, an organic EL element, an organic thin film transistor, and a solar cell. It can be used as an organic electronic material useful as a member such as a material, an antistatic material, a transparent conductive film, and a solid electrolytic capacitor.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, these are illustrations and the present 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.

First, the measurement method performed in this example will be described.
(Measurement method of weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography (GPC). A sample of 0.007 g was dissolved in formic acid (98%, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) to a total of 7.0 g, and the sample concentration was adjusted to 0.1 mass%, and a 1.5 mL vial was prepared. A bottle was filled and measured under the following conditions.
Equipment: High speed GPC equipment manufactured by Tosoh Corporation HLC-8320GPC
Column: Hydrophilic vinyl polymer fine particle gel system column TSKgelSuperA
WM-H
Eluent: 98% formic acid (Wako Pure Chemical Industries, special grade)
Flow rate: 0.4 mL / min
Column temperature: 40 ° C
Injection volume: 0.1 μL
Detector: Suggested refractive index detector

  The weight average molecular weight is eluted using four types of monodisperse polyethylene oxides having different molecular weights and known molecular weights (standard samples of molecular weights 2,000, 21,000, 44,900, and 101,000 manufactured by Tosoh Corporation). A time-molecular weight calibration curve was prepared, and a weight average molecular weight was calculated on the calibration curve from the corresponding elution time distribution by the GPC analysis program EcoSEC-WS manufactured by Tosoh Corporation.

(Measurement method of UV-visible absorption spectrum)
The UV-visible absorption spectrum was obtained by dissolving 0.01 g of a sample in formic acid (98%, reagent grade), making the whole 8.0 g, and collecting 0.5 g of the solution and further diluting with formic acid. The final sample concentration was 0.01% by mass. The solution is filled in a quartz cell having a thickness of 2 mm, and an ultraviolet-visible absorption spectrum is measured. From the obtained ultraviolet-visible spectrum, an ultraviolet-visible absorption spectrum when a formic acid is filled in a quartz cell having a thickness of 2 mm (blank) is obtained. Obtained by subtracting as background.
Apparatus: JASCO Corporation UV-visible absorption spectrophotometer V-670
Light source: deuterium lamp, halogen lamp Measurement wavelength range: 1100 to 250 nm
Detector: Photomultiplier tube, cooled PbS photoconductive element Band width: 1.0 nm
Scanning speed: 400 nm / min

(CHN analysis)
Using MICRO CORDER JM10 manufactured by J Science Lab Co., Ltd., a sample of 2,500 μg was filled in a sample stage, and CHN analysis was performed. 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.

[Example 1]
9 g of acetic acid and 99 g of water were mixed, and 72 g of hydrocyanic acid was mixed with this to obtain a hydrocyanic acid solution containing acid. Furthermore, 14 g of 25% aqueous ammonia was prepared.

  All operations were performed in a glove box with an exhaust device installed in the draft. A 300 mL SUS beaker was covered with a five-neck glass cover and fixed. A stirring blade was set in the middle tube, and a thermometer, pH meter, dropping funnel and cooling tube were set in the side tube. The stirring blade was connected to an air driven stirrer. The cooling pipe was connected to an empty trap and then to an alkali trap so that the inside of the reactor was not pressurized. A mixed solution of water and antifreeze was passed through the cooling pipe and cooled from -5 ° C to -10 ° C. The whole was fixed so that the lower part of the reactor was immersed in the water bath. The acid-containing hydrocyanic acid solution was charged into the reactor using a dropping burette. The reaction solution was heated in a water bath, and the aqueous ammonia was added using a dropping burette when the solution temperature reached 30 ° C. 10 minutes after the addition of ammonia water, the water bath temperature is set to 40 ° C., and then the hydrocyanic acid concentration is 50% at 20% or less, 60 ° C. at 10% or less, 70 ° C. at 5% or less, 80 ° C. at 2% or less. The reaction temperature was adjusted. During the reaction process, no sudden exotherm or explosion was observed. After 7 hours, the reactor was removed from the water bath, the cover was removed, and the dark brown solid was manufactured by ADVANTEC, model no. The sample was collected by suction filtration using 5C (retained particle diameter 1 μm (catalog value)) filter paper. The collected black-brown solid was washed with dimethyl sulfoxide, then washed with water and acetone, and dried under reduced pressure at 120 ° C. After confirming that water and hydrocyanic acid did not remain, the weight was measured, and the yield was calculated from the charged hydrocyanic acid weight. 37.4 g of cyanide polymer was recovered. The yield was 51.9%. Since N / C was high and a π-conjugated structure was developed, it was estimated that a cyanide polymer containing a large amount of C═N conjugated bonds was obtained.

[Example 2]
The same operation as in Example 1 was performed except that the amount of ammonia water was changed to 20 g. When a polymerization reaction was carried out by filling the reactor with the above-mentioned hydrocyanic acid / acid mixture and aqueous ammonia, no rapid heat generation or explosion was observed in the reaction process, and 50.5 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 70.1%.

[Example 3]
The same operation as in Example 1 was performed except that the amount of ammonia water was changed to 28 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid / acid and aqueous ammonia into the reactor, no sudden heat generation or explosion was observed in the reaction process, and 60.1 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 83.5%.

[Example 4]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 48 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no rapid heat generation or explosion was observed in the reaction process, and 67.3 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 93.5%.

[Example 5]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 48 g and that the temperature was maintained when the reaction temperature was raised to 60 ° C. When the polymerization reaction was carried out by filling the reactor with the above-mentioned hydrocyanic acid / acid mixture and aqueous ammonia, no rapid heat generation or explosion was observed in the reaction process, and 22.3 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 31.0%.

[Example 6]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 48 g and that the reaction temperature was raised to 120 ° C. and the total pressure was maintained at 0.2 MPa. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid / acid and aqueous ammonia into the reactor, no rapid heat generation or explosion was observed in the reaction process, and 64.8 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 90.0%.

[Example 7]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 84 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no rapid heat generation or explosion was observed in the reaction process, and 62.0 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 86.1%.

[Example 8]
The same operation as in Example 1 was performed except that the amount of ammonia water was changed to 120 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid / acid and aqueous ammonia into the reactor, no sudden heat generation or explosion was observed in the reaction process, and 58.2 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 80.8%.

[Example 9]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 192 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid / acid and aqueous ammonia into the reactor, no sudden heat generation or explosion was observed in the reaction process, and 25.2 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 35.0%.

[Example 10]
The same operation as in Example 1 was performed except that the amount of acetic acid was changed to 27 g and the amount of aqueous ammonia was changed to 40 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, rapid exothermic heat and explosion were not observed in the reaction process, and 35.4 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 49.2%.

[Example 11]
The same operation as in Example 1 was performed except that the amount of acetic acid was changed to 27 g and the amount of aqueous ammonia was changed to 56 g. When the polymerization reaction was carried out by filling the reactor with the above-mentioned hydrocyanic acid / acid mixture and aqueous ammonia, rapid exothermic heat and explosion were not observed in the reaction process, and 45.3 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 62.9%.

[Example 12]
The same operation as in Example 1 was performed except that the amount of acetic acid was changed to 27 g and the amount of aqueous ammonia was changed to 72 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no sudden heat generation or explosion was observed in the reaction process, and 51.1 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 71.0%.

[Example 13]
The same operation as in Example 1 was performed except that 33 g of diethylamine was used instead of ammonia water. When a polymerization reaction was carried out by filling the reactor with the above-mentioned mixture of hydrocyanic acid and diethylamine, no sudden heat generation or explosion was observed in the reaction process, and 58.2 g of hydrocyanic acid polymer was recovered after 7 hours. . The yield was 80.8%.

[Example 14]
The same operation as in Example 1 was performed except that 55 g of diethylamine was used instead of ammonia water. When a polymerization reaction was carried out by filling the reactor with the above-mentioned hydrocyanic acid / acid mixture and diethylamine, no rapid heat generation or explosion was observed in the reaction process, and 65.9 g of hydrocyanic acid polymer was recovered after 7 hours. . The yield was 91.5%.

[Example 15]
The same operation as in Example 1 was performed except that 45 g of triethylamine was used instead of ammonia water. When the polymerization reaction was carried out by charging the above-mentioned mixed solution of trihydric acid and triethylamine into the reactor, rapid exotherm, explosion, etc. were not observed in the reaction process, and 58.7 g of the cyanic acid polymer was recovered after 7 hours. . The yield was 81.5%.

[Example 16]
The same operation as in Example 1 was performed except that 4 g of sulfuric acid was used instead of acetic acid. When the polymerization reaction was carried out by filling the reactor with the above mixture of hydrocyanic acid / acid and aqueous ammonia, no sudden heat generation or explosion was observed in the reaction process, and 60.7 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 84.3%.

[Example 17]
The same operation as in Example 1 was performed except that 4 g of sulfuric acid was used instead of acetic acid, 33 g of diethylamine was used instead of ammonia water, and no ammonia water was used. When a polymerization reaction was carried out by filling the reactor with the above-mentioned mixture of hydrocyanic acid and acid and diethylamine, no sudden heat generation or explosion was observed in the reaction process, and 59.2 g of the hydrocyanic acid polymer was recovered after 7 hours. . The yield was 82.2%.

[Example 18]
The same operation as in Example 1 was performed except that 41 g of diethylethylenediamine was used instead of ammonia water. When the polymerization reaction was carried out by filling the reactor with the above-mentioned mixture of cyanic acid and acid and diethylethylenediamine, no sudden heat generation or explosion was observed in the reaction process, and 26.4 g of cyanide polymer was recovered after 7 hours. did. The yield was 33.0%.

[Comparative Example 1]
72 g of cyanic acid not containing an acid and 108 g of water were prepared and mixed to obtain an aqueous hydrocyanic acid solution. The above mixed liquid was stored in a sealed container without using a base. Coloring was observed after 1 month and an increase in internal pressure was observed. Cyanic acid polymer could not be recovered.

[Comparative Example 2]
72 g of cyanic acid containing no acid and 55 g of diethylamine were prepared and mixed. The mixed liquid was stored in a sealed container. After several minutes, coloring was observed, and after 1 hour, formation of a blackish brown solid and an increase in internal pressure were observed. After 5 hours, a popping sound started to occur in the sealed container, and the container valve was opened at this stage. 60 g of a blackish brown solid was recovered from the container. The black-brown solid was mostly dissolved when washed with dimethyl sulfoxide. The dissolved component is considered to be an oligomer with a low degree of polymerization. Finally, the remaining black powder was dried under reduced pressure at 120 ° C., and 1.2 g of cyanide polymer was recovered. The yield was 1.7%.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the amount of ammonia water was changed to 10 g. When the polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and diethylamine into the reactor, the color gradually changed to yellow in one week, but the hydrocyanic acid polymer could not be recovered.

[Comparative Example 4]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 12 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no sudden heat generation or explosion was observed in the reaction process, and 0.7 g of hydrocyanic acid polymer was recovered after 7 hours. did. The yield was 1.0%.

[Comparative Example 5]
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was changed to 246 g. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no rapid heat generation or explosion was observed in the reaction process, and 3.6 g of cyanide polymer was recovered after 7 hours. did. The yield was 5.0%.

[Comparative Example 6]
The same operation as in Example 1 was performed except that 274 g of diethylamine was used instead of ammonia water. When a polymerization reaction was carried out by charging the above-mentioned mixture of hydrocyanic acid and acid and aqueous ammonia into the reactor, no rapid heat generation or explosion was observed in the reaction process, and 2.4 g of cyanide polymer was recovered after 7 hours. did. The yield was 3.3%.

  Table 1 shows the polymerization reaction conditions and the physical properties of the polymers in Examples 1 to 15, Reference Example 1 and Comparative Examples 1 to 6.

  FIG. 1 shows a graph comparing the ultraviolet-visible absorption spectrum of the cyanide polymer obtained in Example 1 with the ultraviolet-visible absorption spectrum of the cyanate polymer (black brown solid sample) obtained in Comparative Example 2. In the figure, the thick line shows the absorption spectrum of Example 1, and the thin line shows the absorption spectrum of Comparative Example 2. As shown in FIG. 1, it was shown that the cyanide polymer obtained in Example 1 had higher absorption strength than that in Comparative Example 2 and the conjugated structure was sufficiently developed.

  FIG. 2 shows a graph comparing the ultraviolet-visible absorption spectrum of the cyanide polymer obtained in Example 15 with the ultraviolet-visible absorption spectrum of the cyanate polymer (black brown solid sample) obtained in Comparative Example 2. In the figure, the thick line shows the absorption spectrum of Example 15, and the thin line shows the absorption spectrum of Comparative Example 2. As shown in FIG. 2, it was shown that the cyanide polymer obtained in Example 15 had higher absorption strength than that of Comparative Example 2 and the conjugated structure was sufficiently developed.

  A graph showing the relationship between the x value in the formula (I) and the yield of the cyanide polymer is shown in FIG. As shown in FIG. 3, it can be seen that when X is 1 or more and 20 or less, the yield of the cyanide polymer is increased.

  The method for producing a cyanide polymer according to the present invention is an industrial process for producing a cyanide polymer that can be used as a precursor of a nitrogen-containing carbon material such as a lithium ion secondary battery negative electrode, a capacitor electrode, and a redox catalyst for a fuel cell electrode. With the above applicability. It is also used in the manufacture of cyanide polymers that can be used as conductive polymer materials, electric double layer capacitors, organic EL elements, organic thin film transistors, solar cell materials, antistatic materials, transparent conductive films, solid electrolytic capacitors, etc. as organic electronic materials. With the above applicability.

Claims (4)

  A cyanide polymer having an absorption intensity of light having a wavelength of 600 nm of 0.10 or more in an ultraviolet-visible absorption spectrum of a 0.01% by mass formic acid solution.   The cyanide polymer according to claim 1, wherein the weight average molecular weight is 5,000 or more.   The cyanide polymer of Claim 1 or 2 whose molar ratio (N / C) of the nitrogen atom with respect to a carbon atom is 0.8-1.0. The step 1 and the step include the step 1 of mixing an acid and a hydrocyanic acid to obtain a hydrocyanic acid containing an acid, and the step 2 of mixing a hydrocyanic acid and a base containing the acid to obtain a hydrocyanic acid polymer. The x value of the following formula (I) satisfies 1 or more and 20 or less when the number of moles of the acid is a, the number of moles of the hydrocyanic acid is b, and the number of moles of the base is c. The manufacturing method of the cyanide polymer of 1-3.
x = c / (a + 0.01 × b) (I)