WO2020008828A1 - Composé diamine et son procédé de production - Google Patents

Composé diamine et son procédé de production Download PDF

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Publication number
WO2020008828A1
WO2020008828A1 PCT/JP2019/023398 JP2019023398W WO2020008828A1 WO 2020008828 A1 WO2020008828 A1 WO 2020008828A1 JP 2019023398 W JP2019023398 W JP 2019023398W WO 2020008828 A1 WO2020008828 A1 WO 2020008828A1
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WO
WIPO (PCT)
Prior art keywords
general formula
compound
mass
amino
benzoxazole
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Ceased
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PCT/JP2019/023398
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English (en)
Japanese (ja)
Inventor
俊之 戸田
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2020528759A priority Critical patent/JPWO2020008828A1/ja
Priority to CN201980038625.8A priority patent/CN112243436A/zh
Publication of WO2020008828A1 publication Critical patent/WO2020008828A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals

Definitions

  • the present invention relates to a high-purity diamine compound and a method for producing the same. More specifically, the present invention relates to a highly pure diamine compound having a benzoxazole structure and a method for producing the same.
  • a diamine compound having a benzoxazole structure is a useful compound used as a monomer for a polyimide film or a curing agent for an epoxy compound.
  • a method for producing a diamine compound having a benzoxazole structure a method for reducing a corresponding dinitro compound is known (Patent Document 1).
  • this method has a problem that a coloring substance is generated during reduction, and the diamine compound obtained after the reaction is colored yellow to brown.
  • a method of suppressing this coloring a method of using an adsorbent such as activated carbon together with a reducing agent has been proposed (Patent Document 2).
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a diamine compound which is not colored not only immediately after production but also when stored for a long period of time, and a method for producing the same. Furthermore, by using a sulfur-containing compound as the reducing agent, it can be produced industrially and safely.
  • the present inventors have completed the present invention by the following method. That is, the present invention has the following configurations.
  • the sulfur content is 1 to 100 ppm
  • the total amount of the compound represented by the following general formula (2) and the compound represented by the following general formula (4) is 0.01 to 1% by mass
  • the purity is 99% by mass or more.
  • a diamine compound represented by the general formula (1) a plurality of R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 3 carbons.
  • M is an integer of 1 to 3, and n is 1 to 4; It is an integer.
  • R 1 , R 2 , m and n have the same meanings as described above.
  • R 3 and R 4 each independently represent NO 2 , NO or NHOH, provided that R 3 and R both 4 excluding the case of NO 2.
  • R 1 , R 2 , m and n have the same meanings as described above.
  • X represents hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • R 1 , R 2 , m and n are as defined above.
  • the sulfur-containing compound is preferably at least one compound selected from the group consisting of sulfur, hydrogen sulfide, alkali metal sulfide and alkali metal hydrogen sulfide.
  • the diamine compound of the present invention is not colored not only immediately after production, but also when stored for a long period of time. Therefore, the diamine compound can be stored for a long period of time, and neither the polyimide film nor the epoxy cured product is colored even when used as a monomer of the polyimide film or a curing agent for the epoxy compound. Furthermore, by using a sulfur-containing compound as the reducing agent, it can be produced industrially and safely.
  • the diamine compound represented by the general formula (1) has a benzoxazole structure.
  • a plurality of R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. Specifically, it is hydrogen, methyl, ethyl, n-propyl or isopropyl, preferably hydrogen or methyl, and more preferably hydrogen.
  • m is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
  • n is an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
  • the substitution position of NH 2 (amino group) on the benzoxazole ring may be any of the 4-position, 5-position, 6-position or 7-position, but the 5-position or 6-position Is more preferred, and more preferably the 5-position.
  • the substitution position of NH 2 (amino group) in the phenyl group may be any of the 2-, 3- or 4-position, but is preferably the 3- or 4-position, more preferably the 4-position.
  • the compound of the general formula (1) include, but are not particularly limited to, 4-amino-2- (2-aminophenyl) benzoxazole, 5-amino-2- (2-aminophenyl) benzoxazole, Amino-2- (2-aminophenyl) benzoxazole, 7-amino-2- (2-aminophenyl) benzoxazole, 4- or 6- or 7-methyl-5-amino-2- (2-aminophenyl) Benzoxazole, 4- or 5- or 7-methyl-6-amino-2- (2-aminophenyl) benzoxazole, 5-amino-2- (2-amino-3-methylphenyl) benzoxazole, 5-amino -2- (2-amino-4-methylphenyl) benzoxazole, 5-amino-2- (2-amino-5-methylphenyl) benzoxazole , 5-amino-2- (2-amino-6-methylphenyl) benzox
  • 5-amino-2- (4-aminophenyl) benzoxazole is preferred.
  • Polyimide films made using 5-amino-2- (4-aminophenyl) benzoxazole are excellent in heat resistance and flexibility, so that they can be used for information communication equipment (broadcasting equipment, mobile radio, portable communication equipment, etc.), It can be suitably used for flexible electronic devices such as radars and high-speed information processing devices.
  • the compound of the general formula (1) can be produced by reducing a dinitro compound represented by the general formula (3) (hereinafter, also simply referred to as a compound of the general formula (3)).
  • the compound of the general formula (3) is a compound corresponding to the compound of the general formula (1), and R 1 , R 2 , m and n have the same meaning as in the general formula (1).
  • the reaction proceeds via a compound represented by the general formula (2) (hereinafter, also referred to as a compound of the general formula (2) or an intermediate).
  • a compound represented by the general formula (2) hereinafter, also referred to as a compound of the general formula (2) or an intermediate.
  • the intermediate since the intermediate is not completely consumed (reduced), a small amount The intermediate is mixed into the compound of the general formula (1).
  • the compound of the general formula (3) can be synthesized via an intermediate amide by a reaction between a corresponding aminonitrophenol and nitrochlorobenzoic acid. This is represented by the following equation when represented by a reaction equation.
  • the intermediate amide is dehydrated and condensed with polyphosphoric acid to synthesize the compound of the general formula (3).
  • the intermediate amide is not completely consumed (dehydration condensation), a small amount of the intermediate amide remains. However, it is mixed into the compound of the general formula (3).
  • the compound of the general formula (3) containing a trace amount of the intermediate amide is reduced, the intermediate amide is similarly reduced to a compound of the general formula (4).
  • the compound of 4) is mixed.
  • the compound of the general formula (4) (hereinafter referred to as solvolyzed product) can also be obtained by solvolysis (hydrolysis) of the compound of the general formula (1) once formed. ) May be generated.
  • solvolysis hydrolysis
  • the compound of the general formula (4) is a keto-enol tautomer. This is represented by the following equation when represented by a reaction equation.
  • the present inventors have found that the compound of the general formula (1) itself is oxidized and colored with time, and the compound of the general formula (2) and the compound of the general formula (4) mixed in a trace amount also become colored with time.
  • the coloring is accelerated, and the incorporation of a trace amount of activated carbon promotes the coloring.
  • a sulfur-containing compound is preferable.
  • the sulfur-containing compound is not particularly limited, but is preferably at least one compound selected from the group consisting of sulfur, hydrogen sulfide, alkali metal sulfide and alkali metal hydrogen sulfide.
  • the alkali metal salt in the alkali metal sulfide or alkali metal sulfide include a lithium salt, a sodium salt, and a potassium salt, and a sodium salt is preferable.
  • sodium sulfide or sodium hydrogen sulfide sodium hydrosulfide
  • sodium hydrogen sulfide sodium hydrosulfide
  • the reducing agent is preferably at least 3 mol, more preferably at least 3.5 mol, even more preferably at least 4 mol, per 1 mol of the compound of the formula (3).
  • the amount is too small, the compound of the general formula (3) is not sufficiently reduced, a large amount of the intermediate remains, or the sulfur content of the compound of the general formula (1) is reduced, so that coloring over time can be suppressed. May disappear. Further, it is preferably at most 10 mol, more preferably at most 8 mol, further preferably at most 6 mol. If the amount is too large, the sulfur content of the compound of the general formula (1) becomes too large, and when the polyimide film is used for a flexible electronic device, the migration phenomenon may be increased.
  • the sulfur content of the compound of the general formula (1) needs to be 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, and still more preferably 20 ppm or more. If the amount is too small, the coloring of the compound of the general formula (1), the compound of the general formula (2) and the compound of the general formula (4) with time may not be suppressed. Further, it is necessary to be 100 ppm or less, preferably 80 ppm or less, more preferably 60 ppm or less, and still more preferably 50 ppm or less. If the amount is too large, the migration phenomenon may increase when a polyimide film produced from the compound of the general formula (1) is used for a flexible electronic device.
  • the compound of formula (2) (intermediate) is a compound corresponding to the compound of formula (1), and R 1 , R 2 , m and n have the same meaning as in formula (1).
  • R 3 and R 4 each independently represent NO 2 , NO or NHOH. However, this excludes the case where both R 3 and R 4 are NO 2 .
  • the compound of the general formula (2) is not particularly limited as long as it is a compound obtained by reducing the general formula (1), and examples thereof include compounds represented by the formulas (A) to (K).
  • the formulas (A) to (K) exemplify a compound (an intermediate of 5-amino-2- (4-aminophenyl) benzoxazole) substituted at the 2-position of the benzoxazole ring and the 4-position of the phenyl group.
  • compounds at other substitution positions can be exemplified in the same manner.
  • the amount of the compound of the general formula (2) in the compound of the general formula (1) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. , More preferably 0.05% by mass or less, particularly preferably 0.03% by mass or less. If the amount is too large, the purity of the compound of the general formula (1) may decrease, and the compound may be colored with time.
  • the lower limit is not particularly limited, but is sufficient if it is 0.005% by mass or more, may be 0.01% by mass or more, and may be 0.02% by mass or more.
  • the content of the compound of the general formula (2) refers to the total amount of all reduced compounds.
  • the compound of the general formula (4) is a compound corresponding to the compound of the general formula (1), and R 1 , R 2 , m and n have the same meaning as in the general formula (1). Further, the substitution positions of NH 2 (amino group), R 1 and R 2 are the same positions that are chemically allowed with the compound of the general formula (1).
  • the amount of the compound of the general formula (4) in the compound of the general formula (1) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. , More preferably 0.05% by mass or less, particularly preferably 0.03% by mass or less. If the amount is too large, the purity of the compound of the general formula (1) may decrease, and the compound may be colored with time.
  • the lower limit is not particularly limited, but is sufficient if it is 0.005% by mass or more, may be 0.01% by mass or more, and may be 0.02% by mass or more.
  • the total amount of the compound represented by the general formula (2) and the compound represented by the following general formula (4) needs to be 1% by mass or less, preferably 0.5% by mass. %, More preferably 0.1% by mass or less, further preferably 0.05% by mass or less, particularly preferably 0.03% by mass or less. If the amount is too large, the purity of the compound of the general formula (1) may decrease, and the compound may be colored with time.
  • the lower limit is not particularly limited, and is sufficient if it is 0.01% by mass or more, and may be 0.02% by mass or more.
  • the purity of the compound of the general formula (1) needs to be 99% by mass or more. It is preferably at least 99.5% by mass, more preferably at least 99.9% by mass, further preferably at least 99.95% by mass, particularly preferably at least 99.97% by mass.
  • the upper limit is preferably 100% by mass, but industrially 99.99% by mass is sufficient.
  • Solvents that can be used in the reduction reaction include water solvents; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as diethyl ether, cyclohexylmethyl ether, dibutyl ether, dimethoxyethane, dioxane, tetrahydrofuran, and dioxolane; Solvents such as toluene, xylene, benzene and hexane; chlorine solvents such as chloroform, dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene; N, N-dimethyl Formamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide; and the like.
  • the solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is not particularly limited and may be appropriately set.
  • the concentration of the compound of the general formula (3) is preferably about 0.01 to 10 mol / L.
  • the concentration is 0.05 to 5 mol / L, more preferably 0.1 to 1 mol / L.
  • the heating temperature during the reduction reaction is not particularly limited, but is preferably from 20 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, even more preferably from 50 ° C to 100 ° C.
  • the reaction time depends on the heating temperature and the like, but is usually preferably 1 hour or more and 48 hours or less, more preferably 5 hours or more and 30 hours or less.
  • the compound of the general formula (1) of the present invention has a low content of the compound of the general formula (2) and the compound of the general formula (4) which cause coloring, and has high purity. And since it has a predetermined amount of sulfur content, it does not color with time even if stored for a long time. Therefore, the polyimide film produced using the compound of the general formula (1) is not colored, and flexible electronic devices such as information communication equipment (broadcasting equipment, mobile radio, portable communication equipment, etc.), radar, and high-speed information processing equipment. Can be suitably used.
  • the sulfur content was measured by inductively coupled plasma (ICP) emission spectroscopy (Model SII SPS3100). About 0.5 g of a sample is precisely weighed, 2 mL of concentrated hydrochloric acid is added, and the mixture is diluted to 50 mL with ion-exchanged water. A standard solution having a sulfur content of 0 to 0.8 ppm is separately prepared and subjected to ICP analysis to determine the sulfur content in the compound of the general formula (1) from the ratio of the peak intensity to the standard solution.
  • ICP inductively coupled plasma
  • the compound represented by the general formula (2) has a relative retention time (rrt) of 3.35 to 6.72 based on the diamine compound represented by the general formula (1) (retention time: about 2.12 min).
  • the areas at the peak positions were summed. In the present invention, the area is defined as mass%.
  • ⁇ Storage stability> Dissolve 4 g of a sample in a transparent bottle having a capacity of 30 mL with 20 mL of N, N-dimethylacetamide, cover with a white cap, store at 25 ° C. for 1 day, and measure the color tone by a color difference meter (Model Minolta CR300) ).
  • Change in L *
  • Example 1 (Production of 5-amino-2- (4-aminophenyl) benzoxazole) 2-Amino-4-nitrophenol (10.17 g, 0.066 mol) and butyl acetate (350 mL) were charged into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred at room temperature under stirring. 4-Nitrochlorobenzoic acid (12.61 g, 0.068 mol) dissolved in (60 mL) was added dropwise. After heating to 100 ° C and stirring for 4 hours, polyphosphoric acid (15 g) was added, and the mixture was further stirred at 125 ° C for 10 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Le problème à résoudre par la présente invention concerne la fourniture : d'un composé diamine qui ne se décolore pas, non seulement immédiatement après la production mais même lorsqu'il est stocké pendant une période prolongée ; et d'un procédé de production du composé diamine. La présente invention concerne un composé diamine ayant une structure benzoxazole dont la teneur en soufre est de 1 à 100 ppm, la quantité totale d'intermédiaires et de produits solvolysés est de 0,01 à 1 % en masse, et la pureté est de 99 % en masse ou plus.
PCT/JP2019/023398 2018-07-05 2019-06-13 Composé diamine et son procédé de production Ceased WO2020008828A1 (fr)

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JP2020528759A JPWO2020008828A1 (ja) 2018-07-05 2019-06-13 ジアミン化合物およびその製造方法
CN201980038625.8A CN112243436A (zh) 2018-07-05 2019-06-13 二胺化合物及其制造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022044011A (ja) * 2020-09-04 2022-03-16 エスケー イノベーション カンパニー リミテッド 新規なジアミン化合物、その製造方法およびこれを含む組成物

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022044011A (ja) * 2020-09-04 2022-03-16 エスケー イノベーション カンパニー リミテッド 新規なジアミン化合物、その製造方法およびこれを含む組成物

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