WO2013039185A1 - Benzoxazine compound and manufacturing method therefor - Google Patents
Benzoxazine compound and manufacturing method therefor Download PDFInfo
- Publication number
- WO2013039185A1 WO2013039185A1 PCT/JP2012/073558 JP2012073558W WO2013039185A1 WO 2013039185 A1 WO2013039185 A1 WO 2013039185A1 JP 2012073558 W JP2012073558 W JP 2012073558W WO 2013039185 A1 WO2013039185 A1 WO 2013039185A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dihydro
- formula
- group
- benzoxazin
- carbon atoms
- Prior art date
Links
- 0 Cc1c(*)c(*)c(C)c(*)c1* Chemical compound Cc1c(*)c(*)c(C)c(*)c1* 0.000 description 8
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
Definitions
- the present invention relates to a benzoxazine compound and a method for producing the same.
- Ring-opening polymerization proceeds by heating the benzoxazine compound, specifically 2,2-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine) propane, at a low temperature, and the benzoxazine compound is cured and cured. It is known to produce a cured oxazine resin (Japanese Patent Laid-Open No. 2000-178332).
- the present invention includes the following inventions.
- Formula (1) (In the formula, X represents the formula (A-1), the formula (A-2) or the formula (A-3).
- Represents a group represented by R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
- R 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
- Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
- a process comprising reacting a primary amine compound represented by formula and formaldehyde in the presence of a base.
- the compounds of the present invention have the formula (1) (In the formula, X represents the formula (A-1), the formula (A-2) or the formula (A-3).
- R 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
- Preferable X includes a group represented by formula (A-1) or formula (A-2).
- alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group and cyclohexyl group.
- alkyloxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, n-hexyloxy group and cyclohexyloxy group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- phenyl group that may be substituted with an alkyl group having 1 to 4 carbon atoms include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, a 4-isopropylphenyl group, and a 4-t-butylphenyl group. Is mentioned.
- Examples of the compound of the present invention include 1,4-bis (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3). -Phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro- 8-ethyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3 , 4-Dihydro-8-isopropyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene
- the compound of the present invention has the formula (4) (Wherein R 1 to R 6 and X have the same meaning as described above.)
- a bisphenol compound represented by the formula (hereinafter sometimes referred to as bisphenol compound (4)), formula (5) Y 1 —NH 2 (5) (In the formula, Y 1 represents the same meaning as described above.)
- a primary amine compound represented by: Formula (6) Y 2 —NH 2 (6) (Where Y 2 represents the same meaning as described above) Can be produced by a production method including a step of reacting a primary amine compound and formaldehyde represented by the above in the presence of a base.
- Examples of the bisphenol compound (4) include 1,4-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) cyclohexene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1- ( 3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-methyl- 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-ethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-ethyl-4-hydroxyphenyl) ) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-ethyl-4-hydroxyphene) L) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-isopropyl-4-hydroxy
- the bisphenol compound (4) can be produced by the methods described in JP 2002-308808 A, JP 2002-308809 A, and JP 2002-363117 A.
- Examples of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, and n-hexyl. Examples include amines, cyclohexylamine, aniline, o-toluidine, m-toluidine, p-toluidine, 4-isopropylaniline, and 4-t-butylaniline.
- the amount of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) is usually 1 to 20 moles per 1 mole of the bisphenol compound (5), respectively.
- the amount is preferably 1.5 mol to 10 mol, more preferably 1.8 mol to 5 mol.
- Formaldehyde includes formaldehyde aqueous solution, 1,3,5-trioxane, and paraformaldehyde.
- the amount of formaldehyde used is usually 2 to 100 moles, preferably 3 to 20 moles, more preferably 3.5 to 10 moles with respect to 1 mole of the bisphenol compound (4). .
- Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate; triethylamine, diisopropylethylamine, dipropylamine, dibutylamine, tributylamine, pyrrolidine, piperidine, diamylamine, dicyclohexylamine, tripropylamine and 1,8-diazabicyclo [5,4 , 0] secondary or tertiary amines such as undec-7-ene; basic nitrogen-containing heterocyclic compounds such as pyridine and imidazole.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide
- alkali metal carbonates such as sodium carbon
- the amount of the base used is usually from 0.001 mol to 100 mol, preferably from 0.005 mol to 20 mol, more preferably from 0.01 mol to 1 mol, relative to 1 mol of the bisphenol compound (4). 10 moles.
- the base When the base is a liquid, the base may be used as a solvent, and the amount of the base used in that case is not particularly limited.
- the reaction is usually carried out in the presence of a solvent. The solvent may be refluxed during the reaction.
- Solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, n-hexyl alcohol and cyclohexyl alcohol; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; aliphatics such as toluene, xylene and benzene Hydrocarbon solvents; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethyl sulfoxide; nitrile solvents such as acetonitrile and benzonitrile; dichloromethane, chloroform, 1,2- Halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride and chlorobenzene; water; and the like.
- alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, n-
- the solvent a plurality of types of solvents may be mixed and used. Further, as described above, a base may be used as a solvent.
- the reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
- the reaction temperature is usually 0 ° C. to 150 ° C., preferably 20 ° C. to 120 ° C., and more preferably 40 ° C. to 100 ° C.
- the reaction can be followed by measurement such as liquid chromatography. It is preferable to carry out the reaction until an increase in the compound of the present invention or a decrease in the bisphenol compound (4) is not observed.
- the reaction time is usually 1 hour to 100 hours.
- the compound of the present invention can be obtained by subjecting the resulting reaction mass to concentration treatment and / or filtration treatment.
- the taken-out compound of the present invention can be further purified by ordinary purification means such as washing with a solvent and recrystallization.
- the resin cured product of the present invention is obtained by thermally curing the compound of the present invention.
- the resin cured product of the present invention may be a resin cured product obtained by curing one kind of the compound of the present invention, or a resin cured product obtained by curing a mixture of two or more different compounds of the present invention. It may be a thing.
- the method for producing the cured resin product of the present invention (a) a method in which the compound of the present invention is heated to a predetermined temperature and cured, (b) the compound of the present invention is heated and melted and poured into a mold, etc. Examples include a method in which the mold is further heated and cured, and (c) a method in which a melt of the compound of the present invention is injected into a preheated mold and cured.
- ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened
- the thermal diffusivity was measured by the TWA method (thermal phase diffusivity measuring device, Eye Phase Mobile, manufactured by Eye Phase Co., Ltd.).
- Example 1 5.00 g of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 0.092 g of potassium hydroxide, 10.0 g of methanol and 3.37 g of aniline were charged to an internal temperature of 5 ° C. After cooling and charging 5.88 g of 37% aqueous formaldehyde solution, the mixture was reacted for 23 hours under reflux conditions.
- Example 3 1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1) obtained in Example 1 , 3-Benzoxazin-6-yl) benzene 0.8 g was spread on an aluminum plate and degassed with a vacuum heating apparatus at 170 ° C. for 1 hour 30 minutes. Then, this was heated up to 190 degreeC, and also heat-cured by heat-retaining at 190 degreeC for 4 hours, and the brown benzoxazine resin hardened
- Example 4 3-Benzoxazin-6-yl) cyclohexene was spread on an aluminum plate and degassed with a vacuum heating apparatus at 150 ° C. for 1 hour.
- the present invention it is possible to manufacture and provide a cured benzoxazine resin having a higher thermal conductivity.
- ADVANTAGE OF THE INVENTION it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened
- the cured benzoxazine resin is useful as an insulating material that requires heat dissipation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A benzoxazine compound represented by formula (1) (in which X represents a group represented by formula (A-1), formula (A-2), or formula (A-3); R1 through R25 each independently represent a hydrogen atom, a C1-6 alkyl group, a C1-6 alkyloxy group, a halogen atom, or a cyano group; and Y1 and Y2 each independently represent a C1-6 alkyl group or a phenyl group that may be substituted with a C1-4 alkyl group).
Description
本発明は、ベンゾオキサジン化合物およびその製造方法に関する。
The present invention relates to a benzoxazine compound and a method for producing the same.
ベンゾオキサジン化合物、具体的には、２，２−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン）プロパンを低温加熱することにより開環重合が進行し、硬化してベンゾオキサジン樹脂硬化物を生成することが知られている（特開２０００−１７８３３２号公報）。
Ring-opening polymerization proceeds by heating the benzoxazine compound, specifically 2,2-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine) propane, at a low temperature, and the benzoxazine compound is cured and cured. It is known to produce a cured oxazine resin (Japanese Patent Laid-Open No. 2000-178332).
本発明は、以下の発明を含む。
〔１〕 式（１）
（式中、Ｘは式（Ａ−１）、式（Ａ−２）または式（Ａ−３）
で示される基を表わす。
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物。
〔２〕 式（１）で示されるベンゾオキサジン化合物であって、Ｘが式（Ａ−１）または式（Ａ−２）で示される基であることを特徴とする〔１〕記載のベンゾオキサジン化合物。
〔３〕 式（２）
（式中、Ｒ５は、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される〔１〕又は〔２〕記載のベンゾオキサジン化合物。
〔４〕 式（３）
（式中、Ｒ５は、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される〔１〕又は〔２〕記載のベンゾオキサジン化合物。
〔５〕 〔１〕乃至〔４〕のいずれかの請求項記載のベンゾオキサジン化合物を熱硬化させて得られるベンゾオキサジン樹脂硬化物。
〔６〕 式（１）
（式中、Ｘは下記（Ａ−１）、（Ａ−２）または（Ａ−３）
で示される基を表わす。
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物の製造方法であって、
式（４）
（式中、Ｒ１~Ｒ６およびＸは前記と同じ意味を表わす。）
で示されるビスフェノール化合物、式（５）
Ｙ１−ＮＨ２ （５）
（式中、Ｙ１は前記と同じ意味を表わす。）
で示される１級アミン化合物、
式（６）
Ｙ２−ＮＨ２ （６）
（式中、Ｙ２は前記と同じ意味を表わす）
で示される１級アミン化合物
およびホルムアルデヒドを、塩基の存在下に反応させる工程を含むことを特徴とする製造方法。 The present invention includes the following inventions.
[1] Formula (1)
(In the formula, X represents the formula (A-1), the formula (A-2) or the formula (A-3).
Represents a group represented by
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
[2] A benzoxazine compound represented by formula (1), wherein X is a group represented by formula (A-1) or formula (A-2) Compound.
[3] Formula (2)
(Wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound according to [1] or [2], which is represented by:
[4] Formula (3)
(Wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound according to [1] or [2], which is represented by:
[5] A cured benzoxazine resin obtained by thermally curing the benzoxazine compound according to any one of [1] to [4].
[6] Formula (1)
(In the formula, X is the following (A-1), (A-2) or (A-3)
Represents a group represented by
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A process for producing a benzoxazine compound represented by:
Formula (4)
(Wherein R 1 to R 6 and X have the same meaning as described above.)
A bisphenol compound represented by formula (5)
Y 1 —NH 2 (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
Y 2 —NH 2 (6)
(Where Y 2 represents the same meaning as described above)
A process comprising reacting a primary amine compound represented by formula and formaldehyde in the presence of a base.
〔１〕 式（１）
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物。
〔２〕 式（１）で示されるベンゾオキサジン化合物であって、Ｘが式（Ａ−１）または式（Ａ−２）で示される基であることを特徴とする〔１〕記載のベンゾオキサジン化合物。
〔３〕 式（２）
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される〔１〕又は〔２〕記載のベンゾオキサジン化合物。
〔４〕 式（３）
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される〔１〕又は〔２〕記載のベンゾオキサジン化合物。
〔５〕 〔１〕乃至〔４〕のいずれかの請求項記載のベンゾオキサジン化合物を熱硬化させて得られるベンゾオキサジン樹脂硬化物。
〔６〕 式（１）
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物の製造方法であって、
式（４）
で示されるビスフェノール化合物、式（５）
Ｙ１−ＮＨ２ （５）
（式中、Ｙ１は前記と同じ意味を表わす。）
で示される１級アミン化合物、
式（６）
Ｙ２−ＮＨ２ （６）
（式中、Ｙ２は前記と同じ意味を表わす）
で示される１級アミン化合物
およびホルムアルデヒドを、塩基の存在下に反応させる工程を含むことを特徴とする製造方法。 The present invention includes the following inventions.
[1] Formula (1)
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
[2] A benzoxazine compound represented by formula (1), wherein X is a group represented by formula (A-1) or formula (A-2) Compound.
[3] Formula (2)
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound according to [1] or [2], which is represented by:
[4] Formula (3)
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound according to [1] or [2], which is represented by:
[5] A cured benzoxazine resin obtained by thermally curing the benzoxazine compound according to any one of [1] to [4].
[6] Formula (1)
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A process for producing a benzoxazine compound represented by:
Formula (4)
A bisphenol compound represented by formula (5)
Y 1 —NH 2 (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
Y 2 —NH 2 (6)
(Where Y 2 represents the same meaning as described above)
A process comprising reacting a primary amine compound represented by formula and formaldehyde in the presence of a base.
本発明の化合物は、式（１）
（式中、Ｘは式（Ａ−１）、式（Ａ−２）または式（Ａ−３）
で示される基を表わす。
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物である。
好ましいＸとしては、式（Ａ−１）または式（Ａ−２）で示される基が挙げられる。
炭素数１~６のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｔ−ブチル基、ｎ−ヘキシル基及びシクロヘキシル基が挙げられる。
炭素数１~６のアルキルオキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｔ−ブトキシ基、ｎ−ヘキシルオキシ基及びシクロヘキシルオキシ基が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。
炭素数１~４のアルキル基で置換されてもよいフェニル基としては、フェニル基、ｏ−トルイル基、ｍ−トルイル基、ｐ−トルイル基、４−イソプロピルフェニル基及び４−ｔ−ブチルフェニル基が挙げられる。
本発明の化合物としては、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１，４−ビス（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−ｔ−ブチル−８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１，４−ビス（３，４−ジヒドロ−８−メチルー３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−ｔ−ブチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１，４−ビス（３，４−ジヒドロ−８−メチルー３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−ｔ−ブチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、及び、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）シクロヘキサンが挙げられる。
本発明の化合物は、式（４）
（式中、Ｒ１~Ｒ６およびＸは前記と同じ意味を表わす。）
で示されるビスフェノール化合物（以下、ビスフェノール化合物（４）と記すことがある）、式（５）
Ｙ１−ＮＨ２ （５）
（式中、Ｙ１は前記と同じ意味を表わす。）
で示される１級アミン化合物、
式（６）
Ｙ２−ＮＨ２ （６）
（式中、Ｙ２は前記と同じ意味を表わす）
で示される１級アミン化合物
及びホルムアルデヒドを、塩基の存在下に反応させる工程を含む製造方法により製造することができる。
ビスフェノール化合物（４）としては、１，４−ビス（４−ヒドロキシフェニル）ベンゼン、１，４−ビス（４−ヒドロキシフェニル）シクロヘキセン、１，４−ビス（４−ヒドロキシフェニル）シクロヘキサン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１，４−ビス（３−メチルー４−ヒドロキシフェニル）ベンゼン、１，４−ビス（３−メチルー４−ヒドロキシフェニル）シクロヘキセン、及び、１，４−ビス（３−メチルー４−ヒドロキシフェニル）シクロヘキサンが挙げられる。
ビスフェノール化合物（４）は、特開２００２−３０８８０８号公報、特開２００２−３０８８０９号公報、及び、特開２００２−３６３１１７に記載される方法により製造することができる。
式（５）で示される１級アミン化合物および式（６）で示される１級アミン化合物としては、メチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、ｔ−ブチルアミン、ｎ−ヘキシルアミン、シクロヘキシルアミン、アニリン、ｏ−トルイジン、ｍ−トルイジン、ｐ−トルイジン、４−イソプロピルアニリン、及び、４−ｔ−ブチルアニリンが挙げられる。
式（５）で示される１級アミン化合物および式（６）で示される１級アミン化合物の使用量は、それぞれ、ビスフェノール化合物（５）１モルに対して、通常１モル~２０モルであり、好ましくは、１．５モル~１０モルであり、より好ましくは、１．８モル~５モルである。
ホルムアルデヒドとしては、ホルムアルデヒド水溶液、１，３，５−トリオキサン、及び、パラホルムアルデヒドが挙げられる。
ホルムアルデヒドの使用量は、ビスフェノール化合物（４）１モルに対して、通常２モル~１００モルであり、好ましくは、３モル~２０モルであり、より好ましくは、３．５モル~１０モルである。
塩基としては、水酸化ナトリウム及び水酸化カリウム等のアルカリ金属水酸化物；水酸化カルシウム及び水酸化バリウム等のアルカリ土類金属水酸化物；炭酸ナトリウム及び炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム及び炭酸水素カリウム等のアルカリ金属炭酸水素塩；トリエチルアミン、ジイソプロピルエチルアミン、ジプロピルアミン、ジブチルアミン、トリブチルアミン、ピロリジン、ピペリジン、ジアミルアミン、ジシクロヘキシルアミン、トリプロピルアミン及び１，８−ジアザビシクロ〔５，４，０〕ウンデセ−７−エン等の、２級アミン又は３級アミン；ピリジン及びイミダゾール等の塩基性含窒素複素環化合物；が挙げられる。
塩基の使用量は、通常ビスフェノール化合物（４）１モルに対して、０．００１モル~１００モルであり、好ましくは、０．００５モル~２０モルであり、より好ましくは、０．０１モル~１０モルである。塩基が液体である場合には、塩基を溶媒として用いてもよく、その場合の塩基の使用量は特に制限されない。
反応は、通常、溶媒の存在下実施される。溶媒は、反応中、還流させておいてもよい。
溶媒としては、メタノール、エタノール、イソプロピルアルコール、ｎ−ブチルアルコール、ｎ−ヘキシルアルコール及びシクロヘキシルアルコール等のアルコール系溶媒；テトラヒドロフラン、ジオキサン及びジメトキシエタン等のエーテル系溶媒；トルエン、キシレン及びベンゼン等の脂肪族炭化水素溶媒；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリジノン及びジメチルスルホキシド等の非プロトン性極性溶媒；アセトニトリル及びベンゾニトリル等のニトリル溶媒；ジクロロメタン、クロロホルム、１，２−ジクロロエタン、四塩化炭素及びクロロベンゼン等のハロゲン化炭化水素溶媒；水；等が挙げられる。
溶媒は、複数種類の溶媒を混合して用いてもよい。また、上述のとおり、塩基を溶媒として用いてもよい。
反応は、常圧条件下で行ってもよいし、加圧条件下で行ってもよいし、減圧条件下で行ってもよい。また、窒素ガス及びアルゴンガス等の不活性ガス雰囲気下で行ってもよい。
反応温度は、通常０℃~１５０℃であり、好ましくは、２０℃~１２０℃であり、より好ましくは、４０℃~１００℃である。
反応は、液体クロマトグラフィー等の測定により追跡することができる。本発明の化合物の増加またはビスフェノール化合物（４）の減少が認められなくなるまで反応を行うことが好ましい。反応時間は、通常１時間~１００時間である。
反応の終了後、得られた反応マスを濃縮処理および／またはろ過処理することにより、本発明の化合物を得ることができる。取り出された本発明の化合物は、溶媒での洗浄や再結晶等の通常の精製手段より、更に精製することもできる。
本発明の樹脂硬化物は、本発明の化合物を熱硬化させて得られる。
本発明の樹脂硬化物は、１種の本発明の化合物を硬化させて得られる樹脂硬化物であってもよく、異なる２種以上の本発明の化合物からなる混合物を硬化させて得られる樹脂硬化物であってもよい。
本発明の樹脂硬化物の製造方法としては、（ａ）本発明の化合物を所定の温度まで加熱して硬化させる方法、（ｂ）本発明の化合物を加熱融解させて金型等に注ぎ、金型を更に加熱して硬化成型させる方法、（ｃ）本発明の化合物の溶融物を予め加熱された金型に注入して硬化させる方法等が挙げられる。
本発明によれば、より高い熱伝導率を有するベンゾオキサジン樹脂硬化物を製造するために用いられる原料となるベンゾオキサジン化合物およびその製造方法を提供することが可能である。 The compounds of the present invention have the formula (1)
(In the formula, X represents the formula (A-1), the formula (A-2) or the formula (A-3).
Represents a group represented by
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
It is a benzoxazine compound shown by.
Preferable X includes a group represented by formula (A-1) or formula (A-2).
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group and cyclohexyl group.
Examples of the alkyloxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, n-hexyloxy group and cyclohexyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the phenyl group that may be substituted with an alkyl group having 1 to 4 carbon atoms include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, a 4-isopropylphenyl group, and a 4-t-butylphenyl group. Is mentioned.
Examples of the compound of the present invention include 1,4-bis (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3). -Phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro- 8-ethyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3 , 4-Dihydro-8-isopropyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene , 1- (3,4-dihydro-8- -Butyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3 4-dihydro-8-cyclohexyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1,4-bis (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4 -Toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) benzene, 1- (3 , 4-Dihydro-8-methyl-3- (3- Ruyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) benzene, 1- (3 4-Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3-benzo Oxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro -3- (4-Isopropylphenyl) -1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4-t-butylphenyl) -1,3 -Benzoxazin-6-yl) -4- (3,4-dihydride) Rho-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3,8-dimethyl-1,3-benzoxazine-6- Yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-ethyl-8-methyl-1,3-benzo Oxazin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-isopropyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-t -Butyl-8-methyl-1,3-benzoxazi -6-yl) -4- (3,4-dihydro-3-tert-butyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-cyclohexyl lumine 8-methyl -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazin-6-yl) benzene, 1,4-bis (3,4-dihydro -3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- ( 3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-ethyl-3-phenyl-1,3-benzoxazin-6-yl ) -4- (3,4-Di Dro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-isopropyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-tert-butyl-3-phenyl-1,3-benzoxazine- 6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-cyclohexyl-3-phenyl-1, 3-Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1,4-bis (3,4-dihydro-8- Methyl -3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (4-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (3-toluyl) ) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4 -Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3-benzoxazine -6-yl) cyclohexene, 1- (3,4-di Dro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-isopropylphenyl) -1,3-benzo Oxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (4-tert-butylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4 -Dihydro-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3,8-dimethyl-1,3-benzoxazine-6 -Yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-ethyl-8-methyl-1,3- Benzoxazin-6-yl -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-isopropyl-8-methyl-1,3-benzoxazine -6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-tert-butyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-tert-butyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3 -Cyclohexyl 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazin-6-yl) cyclohexene, 1,4-bis (3 4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl)- 4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-ethyl-3-phenyl-1,3-benzoxazine- 6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-isopropyl-3-phenyl-1, 3-Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-t-butyl -3-F Nyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8 -Cyclohexyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1,4-bis (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-toluyl) -1, 3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8 -Methyl-3- 3-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- ( 3,4-Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3 -Benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4 -Dihydro-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-t-butylphenyl) -1 , 3-Benzoxazin-6-yl ) -4- (3,4-Dihydro-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-3,8-dimethyl-) 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-3-ethyl- 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro -3-isopropyl-8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) cyclohexane, 1- ( 3,4-dihydro-3 t-butyl-8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-t-butyl-1,3-benzoxazin-6-yl) cyclohexane and 1 -(3,4-dihydro-3-cyclohexyl lu 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazine-6- Yl) cyclohexane.
The compound of the present invention has the formula (4)
(Wherein R 1 to R 6 and X have the same meaning as described above.)
A bisphenol compound represented by the formula (hereinafter sometimes referred to as bisphenol compound (4)), formula (5)
Y 1 —NH 2 (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
Y 2 —NH 2 (6)
(Where Y 2 represents the same meaning as described above)
Can be produced by a production method including a step of reacting a primary amine compound and formaldehyde represented by the above in the presence of a base.
Examples of the bisphenol compound (4) include 1,4-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) cyclohexene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1- ( 3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-methyl- 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-ethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-ethyl-4-hydroxyphenyl) ) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-ethyl-4-hydroxyphene) L) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-isopropyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-isopropyl4-hydroxyphenyl) -4- ( 4-hydroxyphenyl) cyclohexene, 1- (3-isopropyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-tert-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) ) Benzene, 1- (3-t-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-t-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane , 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydro Ciphenyl) benzene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexylene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1, Examples include 4-bis (3-methyl-4-hydroxyphenyl) benzene, 1,4-bis (3-methyl-4-hydroxyphenyl) cyclohexene, and 1,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane. .
The bisphenol compound (4) can be produced by the methods described in JP 2002-308808 A, JP 2002-308809 A, and JP 2002-363117 A.
Examples of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, and n-hexyl. Examples include amines, cyclohexylamine, aniline, o-toluidine, m-toluidine, p-toluidine, 4-isopropylaniline, and 4-t-butylaniline.
The amount of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) is usually 1 to 20 moles per 1 mole of the bisphenol compound (5), respectively. The amount is preferably 1.5 mol to 10 mol, more preferably 1.8 mol to 5 mol.
Formaldehyde includes formaldehyde aqueous solution, 1,3,5-trioxane, and paraformaldehyde.
The amount of formaldehyde used is usually 2 to 100 moles, preferably 3 to 20 moles, more preferably 3.5 to 10 moles with respect to 1 mole of the bisphenol compound (4). .
Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate; triethylamine, diisopropylethylamine, dipropylamine, dibutylamine, tributylamine, pyrrolidine, piperidine, diamylamine, dicyclohexylamine, tripropylamine and 1,8-diazabicyclo [5,4 , 0] secondary or tertiary amines such as undec-7-ene; basic nitrogen-containing heterocyclic compounds such as pyridine and imidazole.
The amount of the base used is usually from 0.001 mol to 100 mol, preferably from 0.005 mol to 20 mol, more preferably from 0.01 mol to 1 mol, relative to 1 mol of the bisphenol compound (4). 10 moles. When the base is a liquid, the base may be used as a solvent, and the amount of the base used in that case is not particularly limited.
The reaction is usually carried out in the presence of a solvent. The solvent may be refluxed during the reaction.
Solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, n-hexyl alcohol and cyclohexyl alcohol; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; aliphatics such as toluene, xylene and benzene Hydrocarbon solvents; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethyl sulfoxide; nitrile solvents such as acetonitrile and benzonitrile; dichloromethane, chloroform, 1,2- Halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride and chlorobenzene; water; and the like.
As the solvent, a plurality of types of solvents may be mixed and used. Further, as described above, a base may be used as a solvent.
The reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
The reaction temperature is usually 0 ° C. to 150 ° C., preferably 20 ° C. to 120 ° C., and more preferably 40 ° C. to 100 ° C.
The reaction can be followed by measurement such as liquid chromatography. It is preferable to carry out the reaction until an increase in the compound of the present invention or a decrease in the bisphenol compound (4) is not observed. The reaction time is usually 1 hour to 100 hours.
After completion of the reaction, the compound of the present invention can be obtained by subjecting the resulting reaction mass to concentration treatment and / or filtration treatment. The taken-out compound of the present invention can be further purified by ordinary purification means such as washing with a solvent and recrystallization.
The resin cured product of the present invention is obtained by thermally curing the compound of the present invention.
The resin cured product of the present invention may be a resin cured product obtained by curing one kind of the compound of the present invention, or a resin cured product obtained by curing a mixture of two or more different compounds of the present invention. It may be a thing.
As the method for producing the cured resin product of the present invention, (a) a method in which the compound of the present invention is heated to a predetermined temperature and cured, (b) the compound of the present invention is heated and melted and poured into a mold, etc. Examples include a method in which the mold is further heated and cured, and (c) a method in which a melt of the compound of the present invention is injected into a preheated mold and cured.
ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened | cured material which has higher thermal conductivity, and its manufacturing method.
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物である。
好ましいＸとしては、式（Ａ−１）または式（Ａ−２）で示される基が挙げられる。
炭素数１~６のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｔ−ブチル基、ｎ−ヘキシル基及びシクロヘキシル基が挙げられる。
炭素数１~６のアルキルオキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｔ−ブトキシ基、ｎ−ヘキシルオキシ基及びシクロヘキシルオキシ基が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。
炭素数１~４のアルキル基で置換されてもよいフェニル基としては、フェニル基、ｏ−トルイル基、ｍ−トルイル基、ｐ−トルイル基、４−イソプロピルフェニル基及び４−ｔ−ブチルフェニル基が挙げられる。
本発明の化合物としては、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１，４−ビス（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−ｔ−ブチル−８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）ベンゼン、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１，４−ビス（３，４−ジヒドロ−８−メチルー３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−ｔ−ブチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン、１，４−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−エチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−イソプロピル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−ｔ−ブチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−シクロヘキシル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１，４−ビス（３，４−ジヒドロ−８−メチルー３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（３−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（２−トルイル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−イソプロピルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−８−メチル−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−（４−ｔ−ブチルフェニル）−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３，８−ジメチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−メチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−エチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−エチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−イソプロピルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−イソプロピル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、１−（３，４−ジヒドロ−３−ｔ−ブチルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−ｔ−ブチル−１，３−ベンゾオキサジン−６−イル）シクロヘキサン、及び、１−（３，４−ジヒドロ−３−シクロヘキシルー８−メチル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−シクロヘキシル−１，３−ベンゾオキサジン−６−イル）シクロヘキサンが挙げられる。
本発明の化合物は、式（４）
で示されるビスフェノール化合物（以下、ビスフェノール化合物（４）と記すことがある）、式（５）
Ｙ１−ＮＨ２ （５）
（式中、Ｙ１は前記と同じ意味を表わす。）
で示される１級アミン化合物、
式（６）
Ｙ２−ＮＨ２ （６）
（式中、Ｙ２は前記と同じ意味を表わす）
で示される１級アミン化合物
及びホルムアルデヒドを、塩基の存在下に反応させる工程を含む製造方法により製造することができる。
ビスフェノール化合物（４）としては、１，４−ビス（４−ヒドロキシフェニル）ベンゼン、１，４−ビス（４−ヒドロキシフェニル）シクロヘキセン、１，４−ビス（４−ヒドロキシフェニル）シクロヘキサン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−エチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−イソプロピル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−ｔ−ブチル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン、１−（３−シクロヘキシル４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキサン、１，４−ビス（３−メチルー４−ヒドロキシフェニル）ベンゼン、１，４−ビス（３−メチルー４−ヒドロキシフェニル）シクロヘキセン、及び、１，４−ビス（３−メチルー４−ヒドロキシフェニル）シクロヘキサンが挙げられる。
ビスフェノール化合物（４）は、特開２００２−３０８８０８号公報、特開２００２−３０８８０９号公報、及び、特開２００２−３６３１１７に記載される方法により製造することができる。
式（５）で示される１級アミン化合物および式（６）で示される１級アミン化合物としては、メチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、ｔ−ブチルアミン、ｎ−ヘキシルアミン、シクロヘキシルアミン、アニリン、ｏ−トルイジン、ｍ−トルイジン、ｐ−トルイジン、４−イソプロピルアニリン、及び、４−ｔ−ブチルアニリンが挙げられる。
式（５）で示される１級アミン化合物および式（６）で示される１級アミン化合物の使用量は、それぞれ、ビスフェノール化合物（５）１モルに対して、通常１モル~２０モルであり、好ましくは、１．５モル~１０モルであり、より好ましくは、１．８モル~５モルである。
ホルムアルデヒドとしては、ホルムアルデヒド水溶液、１，３，５−トリオキサン、及び、パラホルムアルデヒドが挙げられる。
ホルムアルデヒドの使用量は、ビスフェノール化合物（４）１モルに対して、通常２モル~１００モルであり、好ましくは、３モル~２０モルであり、より好ましくは、３．５モル~１０モルである。
塩基としては、水酸化ナトリウム及び水酸化カリウム等のアルカリ金属水酸化物；水酸化カルシウム及び水酸化バリウム等のアルカリ土類金属水酸化物；炭酸ナトリウム及び炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム及び炭酸水素カリウム等のアルカリ金属炭酸水素塩；トリエチルアミン、ジイソプロピルエチルアミン、ジプロピルアミン、ジブチルアミン、トリブチルアミン、ピロリジン、ピペリジン、ジアミルアミン、ジシクロヘキシルアミン、トリプロピルアミン及び１，８−ジアザビシクロ〔５，４，０〕ウンデセ−７−エン等の、２級アミン又は３級アミン；ピリジン及びイミダゾール等の塩基性含窒素複素環化合物；が挙げられる。
塩基の使用量は、通常ビスフェノール化合物（４）１モルに対して、０．００１モル~１００モルであり、好ましくは、０．００５モル~２０モルであり、より好ましくは、０．０１モル~１０モルである。塩基が液体である場合には、塩基を溶媒として用いてもよく、その場合の塩基の使用量は特に制限されない。
反応は、通常、溶媒の存在下実施される。溶媒は、反応中、還流させておいてもよい。
溶媒としては、メタノール、エタノール、イソプロピルアルコール、ｎ−ブチルアルコール、ｎ−ヘキシルアルコール及びシクロヘキシルアルコール等のアルコール系溶媒；テトラヒドロフラン、ジオキサン及びジメトキシエタン等のエーテル系溶媒；トルエン、キシレン及びベンゼン等の脂肪族炭化水素溶媒；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリジノン及びジメチルスルホキシド等の非プロトン性極性溶媒；アセトニトリル及びベンゾニトリル等のニトリル溶媒；ジクロロメタン、クロロホルム、１，２−ジクロロエタン、四塩化炭素及びクロロベンゼン等のハロゲン化炭化水素溶媒；水；等が挙げられる。
溶媒は、複数種類の溶媒を混合して用いてもよい。また、上述のとおり、塩基を溶媒として用いてもよい。
反応は、常圧条件下で行ってもよいし、加圧条件下で行ってもよいし、減圧条件下で行ってもよい。また、窒素ガス及びアルゴンガス等の不活性ガス雰囲気下で行ってもよい。
反応温度は、通常０℃~１５０℃であり、好ましくは、２０℃~１２０℃であり、より好ましくは、４０℃~１００℃である。
反応は、液体クロマトグラフィー等の測定により追跡することができる。本発明の化合物の増加またはビスフェノール化合物（４）の減少が認められなくなるまで反応を行うことが好ましい。反応時間は、通常１時間~１００時間である。
反応の終了後、得られた反応マスを濃縮処理および／またはろ過処理することにより、本発明の化合物を得ることができる。取り出された本発明の化合物は、溶媒での洗浄や再結晶等の通常の精製手段より、更に精製することもできる。
本発明の樹脂硬化物は、本発明の化合物を熱硬化させて得られる。
本発明の樹脂硬化物は、１種の本発明の化合物を硬化させて得られる樹脂硬化物であってもよく、異なる２種以上の本発明の化合物からなる混合物を硬化させて得られる樹脂硬化物であってもよい。
本発明の樹脂硬化物の製造方法としては、（ａ）本発明の化合物を所定の温度まで加熱して硬化させる方法、（ｂ）本発明の化合物を加熱融解させて金型等に注ぎ、金型を更に加熱して硬化成型させる方法、（ｃ）本発明の化合物の溶融物を予め加熱された金型に注入して硬化させる方法等が挙げられる。
本発明によれば、より高い熱伝導率を有するベンゾオキサジン樹脂硬化物を製造するために用いられる原料となるベンゾオキサジン化合物およびその製造方法を提供することが可能である。 The compounds of the present invention have the formula (1)
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
It is a benzoxazine compound shown by.
Preferable X includes a group represented by formula (A-1) or formula (A-2).
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group and cyclohexyl group.
Examples of the alkyloxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, n-hexyloxy group and cyclohexyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the phenyl group that may be substituted with an alkyl group having 1 to 4 carbon atoms include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, a 4-isopropylphenyl group, and a 4-t-butylphenyl group. Is mentioned.
Examples of the compound of the present invention include 1,4-bis (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3). -Phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro- 8-ethyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3 , 4-Dihydro-8-isopropyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene , 1- (3,4-dihydro-8- -Butyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3 4-dihydro-8-cyclohexyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1,4-bis (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4 -Toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) benzene, 1- (3 , 4-Dihydro-8-methyl-3- (3- Ruyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) benzene, 1- (3 4-Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3-benzo Oxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro -3- (4-Isopropylphenyl) -1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-8-methyl-3- (4-t-butylphenyl) -1,3 -Benzoxazin-6-yl) -4- (3,4-dihydride) Rho-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3,8-dimethyl-1,3-benzoxazine-6- Yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-ethyl-8-methyl-1,3-benzo Oxazin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-isopropyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-t -Butyl-8-methyl-1,3-benzoxazi -6-yl) -4- (3,4-dihydro-3-tert-butyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-cyclohexyl lumine 8-methyl -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazin-6-yl) benzene, 1,4-bis (3,4-dihydro -3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- ( 3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-ethyl-3-phenyl-1,3-benzoxazin-6-yl ) -4- (3,4-Di Dro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-isopropyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-tert-butyl-3-phenyl-1,3-benzoxazine- 6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-cyclohexyl-3-phenyl-1, 3-Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1,4-bis (3,4-dihydro-8- Methyl -3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (4-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (3-toluyl) ) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4 -Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3-benzoxazine -6-yl) cyclohexene, 1- (3,4-di Dro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-isopropylphenyl) -1,3-benzo Oxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (4-tert-butylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4 -Dihydro-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3,8-dimethyl-1,3-benzoxazine-6 -Yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-ethyl-8-methyl-1,3- Benzoxazin-6-yl -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-isopropyl-8-methyl-1,3-benzoxazine -6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-tert-butyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-tert-butyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3 -Cyclohexyl 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazin-6-yl) cyclohexene, 1,4-bis (3 4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl)- 4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-ethyl-3-phenyl-1,3-benzoxazine- 6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-isopropyl-3-phenyl-1, 3-Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-t-butyl -3-F Nyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8 -Cyclohexyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1,4-bis (3,4-dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-toluyl) -1, 3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (4-toluyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8 -Methyl-3- 3-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (3-toluyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- ( 3,4-Dihydro-8-methyl-3- (2-toluyl) -1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3- (2-toluyl) -1,3 -Benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) -4- (3,4 -Dihydro-3- (4-isopropylphenyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-methyl-3- (4-t-butylphenyl) -1 , 3-Benzoxazin-6-yl ) -4- (3,4-Dihydro-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-3,8-dimethyl-) 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-3-ethyl- 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro -3-isopropyl-8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) cyclohexane, 1- ( 3,4-dihydro-3 t-butyl-8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-t-butyl-1,3-benzoxazin-6-yl) cyclohexane and 1 -(3,4-dihydro-3-cyclohexyl lu 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazine-6- Yl) cyclohexane.
The compound of the present invention has the formula (4)
A bisphenol compound represented by the formula (hereinafter sometimes referred to as bisphenol compound (4)), formula (5)
Y 1 —NH 2 (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
Y 2 —NH 2 (6)
(Where Y 2 represents the same meaning as described above)
Can be produced by a production method including a step of reacting a primary amine compound and formaldehyde represented by the above in the presence of a base.
Examples of the bisphenol compound (4) include 1,4-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) cyclohexene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1- ( 3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-methyl- 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-ethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-ethyl-4-hydroxyphenyl) ) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-ethyl-4-hydroxyphene) L) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-isopropyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-isopropyl4-hydroxyphenyl) -4- ( 4-hydroxyphenyl) cyclohexene, 1- (3-isopropyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-tert-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) ) Benzene, 1- (3-t-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-t-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane , 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydro Ciphenyl) benzene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexylene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1, Examples include 4-bis (3-methyl-4-hydroxyphenyl) benzene, 1,4-bis (3-methyl-4-hydroxyphenyl) cyclohexene, and 1,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane. .
The bisphenol compound (4) can be produced by the methods described in JP 2002-308808 A, JP 2002-308809 A, and JP 2002-363117 A.
Examples of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, and n-hexyl. Examples include amines, cyclohexylamine, aniline, o-toluidine, m-toluidine, p-toluidine, 4-isopropylaniline, and 4-t-butylaniline.
The amount of the primary amine compound represented by the formula (5) and the primary amine compound represented by the formula (6) is usually 1 to 20 moles per 1 mole of the bisphenol compound (5), respectively. The amount is preferably 1.5 mol to 10 mol, more preferably 1.8 mol to 5 mol.
Formaldehyde includes formaldehyde aqueous solution, 1,3,5-trioxane, and paraformaldehyde.
The amount of formaldehyde used is usually 2 to 100 moles, preferably 3 to 20 moles, more preferably 3.5 to 10 moles with respect to 1 mole of the bisphenol compound (4). .
Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate; triethylamine, diisopropylethylamine, dipropylamine, dibutylamine, tributylamine, pyrrolidine, piperidine, diamylamine, dicyclohexylamine, tripropylamine and 1,8-diazabicyclo [5,4 , 0] secondary or tertiary amines such as undec-7-ene; basic nitrogen-containing heterocyclic compounds such as pyridine and imidazole.
The amount of the base used is usually from 0.001 mol to 100 mol, preferably from 0.005 mol to 20 mol, more preferably from 0.01 mol to 1 mol, relative to 1 mol of the bisphenol compound (4). 10 moles. When the base is a liquid, the base may be used as a solvent, and the amount of the base used in that case is not particularly limited.
The reaction is usually carried out in the presence of a solvent. The solvent may be refluxed during the reaction.
Solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, n-hexyl alcohol and cyclohexyl alcohol; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; aliphatics such as toluene, xylene and benzene Hydrocarbon solvents; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethyl sulfoxide; nitrile solvents such as acetonitrile and benzonitrile; dichloromethane, chloroform, 1,2- Halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride and chlorobenzene; water; and the like.
As the solvent, a plurality of types of solvents may be mixed and used. Further, as described above, a base may be used as a solvent.
The reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
The reaction temperature is usually 0 ° C. to 150 ° C., preferably 20 ° C. to 120 ° C., and more preferably 40 ° C. to 100 ° C.
The reaction can be followed by measurement such as liquid chromatography. It is preferable to carry out the reaction until an increase in the compound of the present invention or a decrease in the bisphenol compound (4) is not observed. The reaction time is usually 1 hour to 100 hours.
After completion of the reaction, the compound of the present invention can be obtained by subjecting the resulting reaction mass to concentration treatment and / or filtration treatment. The taken-out compound of the present invention can be further purified by ordinary purification means such as washing with a solvent and recrystallization.
The resin cured product of the present invention is obtained by thermally curing the compound of the present invention.
The resin cured product of the present invention may be a resin cured product obtained by curing one kind of the compound of the present invention, or a resin cured product obtained by curing a mixture of two or more different compounds of the present invention. It may be a thing.
As the method for producing the cured resin product of the present invention, (a) a method in which the compound of the present invention is heated to a predetermined temperature and cured, (b) the compound of the present invention is heated and melted and poured into a mold, etc. Examples include a method in which the mold is further heated and cured, and (c) a method in which a melt of the compound of the present invention is injected into a preheated mold and cured.
ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened | cured material which has higher thermal conductivity, and its manufacturing method.
熱拡散率の測定はＴＷＡ法（（株）アイフェイズ製熱拡散率測定装置アイフェイズ・モバイル）により実施した。
実施例１
１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン５．００ｇ、水酸化カリウム０．０９２ｇ、メタノール１０．０ｇ及びアニリン３．３７ｇを仕込み、内温５℃まで冷却し、３７％ホルムアルデヒド水溶液５．８８ｇを仕込んだ後、還流条件下２３時間反応させた。反応終了後、反応液中の不溶分を濾別した後、不溶分をメタノールで洗浄し、真空乾燥することにより、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン６．９９ｇを橙色固体として得た。見かけ収率７５％。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ標準，単位：ｐｐｍ）
δ２．２４（ｓ，３Ｈ），４．７０（ｄ，Ｊ＝５．３Ｈｚ，４Ｈ），５．４４（ｄ，Ｊ＝６．５Ｈｚ，４Ｈ），６．８５~６．９５（ｍ，５Ｈ），７．１４（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．２７（ｔ，Ｊ＝８．１Ｈｚ，４Ｈ），７．３６~７．４３（ｍ，２Ｈ），７．４８~７．５７（ｍ，２Ｈ），７．５６（ｄ，Ｊ＝５．３Ｈｚ，４Ｈ）
実施例２
温度計、冷却管及び撹拌装置を備えた４つ口フラスコに、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン４０．０３ｇ、水酸化カリウム０．５７３ｇ、メタノール１６０ｇ及びアニリン２６．６ｇを仕込み、内温を５０℃以下に保ちながら３７％ホルムアルデヒド水溶液４６．３ｇを仕込んだ後、還流条件下９時間反応させた。反応終了後、反応液中の不溶分を濾別した。得られた不溶分を酢酸エチルに溶解し水で洗浄した後、減圧条件下で濃縮処理することにより、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン５７．２ｇを薄桃色固体として得た。見かけ収率７８％。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ標準，単位：ｐｐｍ）
δ１．７５~１．８６（ｍ，１Ｈ），１．９９~２．１０（ｍ，１Ｈ），２．１７（ｓ，３Ｈ），２．１９~２．３２（ｍ，１Ｈ），２．３６~２．５６（ｍ，２Ｈ），２．６７~２．８２（ｍ，１Ｈ），４．６２（ｄ，Ｊ＝４．９Ｈｚ，４Ｈ），５．３６（ｄ，Ｊ＝１０．３Ｈｚ，４Ｈ），６．０５（ｓ，１Ｈ），６．７６（ｄｄ，Ｊ＝８．４Ｈｚ，２．６Ｈｚ，１Ｈ），６．８９（ｓ，２Ｈ），６．９４（ｄ，Ｊ＝７．３Ｈｚ，２Ｈ），７．０１（ｄｄ，Ｊ＝８．５Ｈｚ，２．１Ｈｚ，１Ｈ），７．０５（ｓ，１Ｈ），７．１２（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），７．２６（ｄｄ，Ｊ＝７．１Ｈｚ，１．８Ｈｚ，４Ｈ）
参考例１
ビスフェノールＡ２０．００ｇおよびアニリン１６．３ｇを、３７％ホルムアルデヒド水溶液２８．４ｇに懸濁したさせた後、得られた懸濁物を６０℃で３０分間、続いて８０℃で２時間反応させた。反応終了後、反応液中の不溶分を濾別した。得られた不溶分をトルエンに溶解させて水で洗浄した後、減圧条件下で濃縮処理することにより、２，２−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン）プロパン３８．５ｇを白色固体として得た。見かけ収率９５％。
実施例３
実施例１で得られた１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン０．８ｇをアルミ板上に広げ、真空加熱装置にて１７０℃で１時間３０分脱気した。その後、これを１９０℃に昇温し、更に１９０℃で４時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１０９μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、１．２１×１０−７ｍ２／ｓであった。
実施例４
実施例２で得られた１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン１ｇをアルミ板上に広げ、真空加熱装置にて１５０℃で１時間脱気した。その後、これを２時間かけ１５０℃から２５０℃に昇温し、さらに２５０℃で１時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１００μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、１．２６×１０−７ｍ２／ｓであった。
比較例１
２，２−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン）プロパン１．５５ｇをアルミ板上に広げ、真空加熱装置にて１５０℃で１時間３０分脱気した。その後、これを２時間かけ１５０℃から２５０℃に昇温し、更に２５０℃で１時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１３１μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、０．９９×１０−７ｍ２／ｓであった。 The thermal diffusivity was measured by the TWA method (thermal phase diffusivity measuring device, Eye Phase Mobile, manufactured by Eye Phase Co., Ltd.).
Example 1
5.00 g of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 0.092 g of potassium hydroxide, 10.0 g of methanol and 3.37 g of aniline were charged to an internal temperature of 5 ° C. After cooling and charging 5.88 g of 37% aqueous formaldehyde solution, the mixture was reacted for 23 hours under reflux conditions. After completion of the reaction, the insoluble matter in the reaction solution was filtered off, and the insoluble matter was washed with methanol and dried under vacuum to give 1- (3,4-dihydro-8-methyl-3-phenyl-1,3. -Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene (6.99 g) was obtained as an orange solid. Apparent yield 75%.
1 H-NMR (CDCl 3 , TMS standard, unit: ppm)
δ 2.24 (s, 3H), 4.70 (d, J = 5.3 Hz, 4H), 5.44 (d, J = 6.5 Hz, 4H), 6.85 to 6.95 (m, 5H) ), 7.14 (d, J = 8.7 Hz, 2H), 7.27 (t, J = 8.1 Hz, 4H), 7.36-7.43 (m, 2H), 7.48-7 .57 (m, 2H), 7.56 (d, J = 5.3 Hz, 4H)
Example 2
In a four-necked flask equipped with a thermometer, a condenser and a stirrer, 40.03 g of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 0.573 g of potassium hydroxide, 160 g of methanol and 26.6 g of aniline were charged, and 46.3 g of a 37% formaldehyde aqueous solution was charged while maintaining the internal temperature at 50 ° C. or lower, and then reacted for 9 hours under reflux conditions. After completion of the reaction, the insoluble matter in the reaction solution was filtered off. 1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazine was obtained by dissolving the obtained insoluble matter in ethyl acetate and washing with water, followed by concentration under reduced pressure. There were obtained 57.2 g of -6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene as a light pink solid. Apparent yield 78%.
1 H-NMR (CDCl 3 , TMS standard, unit: ppm)
δ 1.75 to 1.86 (m, 1H), 1.99 to 2.10 (m, 1H), 2.17 (s, 3H), 2.19 to 2.32 (m, 1H), 2. 36 to 2.56 (m, 2H), 2.67 to 2.82 (m, 1H), 4.62 (d, J = 4.9 Hz, 4H), 5.36 (d, J = 10.3 Hz) , 4H), 6.05 (s, 1H), 6.76 (dd, J = 8.4 Hz, 2.6 Hz, 1H), 6.89 (s, 2H), 6.94 (d, J = 7) .3 Hz, 2 H), 7.01 (dd, J = 8.5 Hz, 2.1 Hz, 1 H), 7.05 (s, 1 H), 7.12 (d, J = 7.8 Hz, 4 H), 7 .26 (dd, J = 7.1 Hz, 1.8 Hz, 4H)
Reference example 1
After suspending 20.00 g of bisphenol A and 16.3 g of aniline in 28.4 g of a 37% aqueous formaldehyde solution, the resulting suspension was reacted at 60 ° C. for 30 minutes and subsequently at 80 ° C. for 2 hours. After completion of the reaction, the insoluble matter in the reaction solution was filtered off. The obtained insoluble matter is dissolved in toluene, washed with water, and then concentrated under reduced pressure to give 2,2-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine). Propane (38.5 g) was obtained as a white solid. Apparent yield 95%.
Example 3
1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1) obtained in Example 1 , 3-Benzoxazin-6-yl) benzene 0.8 g was spread on an aluminum plate and degassed with a vacuum heating apparatus at 170 ° C. for 1 hour 30 minutes. Then, this was heated up to 190 degreeC, and also heat-cured by heat-retaining at 190 degreeC for 4 hours, and the brown benzoxazine resin hardened | cured material was obtained. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain a 109 μm flake, and the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 1.21 × 10 −7 m 2 / s.
Example 4
1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1) obtained in Example 2 , 3-Benzoxazin-6-yl) cyclohexene was spread on an aluminum plate and degassed with a vacuum heating apparatus at 150 ° C. for 1 hour. Thereafter, this was heated from 150 ° C. to 250 ° C. over 2 hours, and further heated and cured at 250 ° C. for 1 hour to obtain a brown benzoxazine resin cured product. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain a 100 μm flake, and the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 1.26 × 10 −7 m 2 / s.
Comparative Example 1
2,5-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine) propane (1.55 g) was spread on an aluminum plate and deaerated at 150 ° C. for 1 hour and 30 minutes using a vacuum heating apparatus. Thereafter, this was heated from 150 ° C. to 250 ° C. over 2 hours, and further heated and cured at 250 ° C. for 1 hour to obtain a brown benzoxazine resin cured product. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain 131 μm flakes, and then the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 0.99 × 10 −7 m 2 / s.
実施例１
１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）ベンゼン５．００ｇ、水酸化カリウム０．０９２ｇ、メタノール１０．０ｇ及びアニリン３．３７ｇを仕込み、内温５℃まで冷却し、３７％ホルムアルデヒド水溶液５．８８ｇを仕込んだ後、還流条件下２３時間反応させた。反応終了後、反応液中の不溶分を濾別した後、不溶分をメタノールで洗浄し、真空乾燥することにより、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン６．９９ｇを橙色固体として得た。見かけ収率７５％。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ標準，単位：ｐｐｍ）
δ２．２４（ｓ，３Ｈ），４．７０（ｄ，Ｊ＝５．３Ｈｚ，４Ｈ），５．４４（ｄ，Ｊ＝６．５Ｈｚ，４Ｈ），６．８５~６．９５（ｍ，５Ｈ），７．１４（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．２７（ｔ，Ｊ＝８．１Ｈｚ，４Ｈ），７．３６~７．４３（ｍ，２Ｈ），７．４８~７．５７（ｍ，２Ｈ），７．５６（ｄ，Ｊ＝５．３Ｈｚ，４Ｈ）
実施例２
温度計、冷却管及び撹拌装置を備えた４つ口フラスコに、１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）シクロヘキセン４０．０３ｇ、水酸化カリウム０．５７３ｇ、メタノール１６０ｇ及びアニリン２６．６ｇを仕込み、内温を５０℃以下に保ちながら３７％ホルムアルデヒド水溶液４６．３ｇを仕込んだ後、還流条件下９時間反応させた。反応終了後、反応液中の不溶分を濾別した。得られた不溶分を酢酸エチルに溶解し水で洗浄した後、減圧条件下で濃縮処理することにより、１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン５７．２ｇを薄桃色固体として得た。見かけ収率７８％。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ標準，単位：ｐｐｍ）
δ１．７５~１．８６（ｍ，１Ｈ），１．９９~２．１０（ｍ，１Ｈ），２．１７（ｓ，３Ｈ），２．１９~２．３２（ｍ，１Ｈ），２．３６~２．５６（ｍ，２Ｈ），２．６７~２．８２（ｍ，１Ｈ），４．６２（ｄ，Ｊ＝４．９Ｈｚ，４Ｈ），５．３６（ｄ，Ｊ＝１０．３Ｈｚ，４Ｈ），６．０５（ｓ，１Ｈ），６．７６（ｄｄ，Ｊ＝８．４Ｈｚ，２．６Ｈｚ，１Ｈ），６．８９（ｓ，２Ｈ），６．９４（ｄ，Ｊ＝７．３Ｈｚ，２Ｈ），７．０１（ｄｄ，Ｊ＝８．５Ｈｚ，２．１Ｈｚ，１Ｈ），７．０５（ｓ，１Ｈ），７．１２（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），７．２６（ｄｄ，Ｊ＝７．１Ｈｚ，１．８Ｈｚ，４Ｈ）
参考例１
ビスフェノールＡ２０．００ｇおよびアニリン１６．３ｇを、３７％ホルムアルデヒド水溶液２８．４ｇに懸濁したさせた後、得られた懸濁物を６０℃で３０分間、続いて８０℃で２時間反応させた。反応終了後、反応液中の不溶分を濾別した。得られた不溶分をトルエンに溶解させて水で洗浄した後、減圧条件下で濃縮処理することにより、２，２−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン）プロパン３８．５ｇを白色固体として得た。見かけ収率９５％。
実施例３
実施例１で得られた１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）ベンゼン０．８ｇをアルミ板上に広げ、真空加熱装置にて１７０℃で１時間３０分脱気した。その後、これを１９０℃に昇温し、更に１９０℃で４時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１０９μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、１．２１×１０−７ｍ２／ｓであった。
実施例４
実施例２で得られた１−（３，４−ジヒドロ−８−メチル−３−フェニル−１，３−ベンゾオキサジン−６−イル）−４−（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン−６−イル）シクロヘキセン１ｇをアルミ板上に広げ、真空加熱装置にて１５０℃で１時間脱気した。その後、これを２時間かけ１５０℃から２５０℃に昇温し、さらに２５０℃で１時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１００μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、１．２６×１０−７ｍ２／ｓであった。
比較例１
２，２−ビス（３，４−ジヒドロ−３−フェニル−１，３−ベンゾオキサジン）プロパン１．５５ｇをアルミ板上に広げ、真空加熱装置にて１５０℃で１時間３０分脱気した。その後、これを２時間かけ１５０℃から２５０℃に昇温し、更に２５０℃で１時間保温して加熱硬化させることにより、褐色のベンゾオキサジン樹脂硬化物を得た。得られた硬化物をサンドペーパー（＃１２００および＃２０００）で表面を研磨して１３１μｍの薄片とした後、ＴＷＡ法により熱拡散率を測定した。その結果、前記硬化物の熱拡散率は、０．９９×１０−７ｍ２／ｓであった。 The thermal diffusivity was measured by the TWA method (thermal phase diffusivity measuring device, Eye Phase Mobile, manufactured by Eye Phase Co., Ltd.).
Example 1
5.00 g of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 0.092 g of potassium hydroxide, 10.0 g of methanol and 3.37 g of aniline were charged to an internal temperature of 5 ° C. After cooling and charging 5.88 g of 37% aqueous formaldehyde solution, the mixture was reacted for 23 hours under reflux conditions. After completion of the reaction, the insoluble matter in the reaction solution was filtered off, and the insoluble matter was washed with methanol and dried under vacuum to give 1- (3,4-dihydro-8-methyl-3-phenyl-1,3. -Benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) benzene (6.99 g) was obtained as an orange solid. Apparent yield 75%.
1 H-NMR (CDCl 3 , TMS standard, unit: ppm)
δ 2.24 (s, 3H), 4.70 (d, J = 5.3 Hz, 4H), 5.44 (d, J = 6.5 Hz, 4H), 6.85 to 6.95 (m, 5H) ), 7.14 (d, J = 8.7 Hz, 2H), 7.27 (t, J = 8.1 Hz, 4H), 7.36-7.43 (m, 2H), 7.48-7 .57 (m, 2H), 7.56 (d, J = 5.3 Hz, 4H)
Example 2
In a four-necked flask equipped with a thermometer, a condenser and a stirrer, 40.03 g of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 0.573 g of potassium hydroxide, 160 g of methanol and 26.6 g of aniline were charged, and 46.3 g of a 37% formaldehyde aqueous solution was charged while maintaining the internal temperature at 50 ° C. or lower, and then reacted for 9 hours under reflux conditions. After completion of the reaction, the insoluble matter in the reaction solution was filtered off. 1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazine was obtained by dissolving the obtained insoluble matter in ethyl acetate and washing with water, followed by concentration under reduced pressure. There were obtained 57.2 g of -6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene as a light pink solid. Apparent yield 78%.
1 H-NMR (CDCl 3 , TMS standard, unit: ppm)
δ 1.75 to 1.86 (m, 1H), 1.99 to 2.10 (m, 1H), 2.17 (s, 3H), 2.19 to 2.32 (m, 1H), 2. 36 to 2.56 (m, 2H), 2.67 to 2.82 (m, 1H), 4.62 (d, J = 4.9 Hz, 4H), 5.36 (d, J = 10.3 Hz) , 4H), 6.05 (s, 1H), 6.76 (dd, J = 8.4 Hz, 2.6 Hz, 1H), 6.89 (s, 2H), 6.94 (d, J = 7) .3 Hz, 2 H), 7.01 (dd, J = 8.5 Hz, 2.1 Hz, 1 H), 7.05 (s, 1 H), 7.12 (d, J = 7.8 Hz, 4 H), 7 .26 (dd, J = 7.1 Hz, 1.8 Hz, 4H)
Reference example 1
After suspending 20.00 g of bisphenol A and 16.3 g of aniline in 28.4 g of a 37% aqueous formaldehyde solution, the resulting suspension was reacted at 60 ° C. for 30 minutes and subsequently at 80 ° C. for 2 hours. After completion of the reaction, the insoluble matter in the reaction solution was filtered off. The obtained insoluble matter is dissolved in toluene, washed with water, and then concentrated under reduced pressure to give 2,2-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine). Propane (38.5 g) was obtained as a white solid. Apparent yield 95%.
Example 3
1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1) obtained in Example 1 , 3-Benzoxazin-6-yl) benzene 0.8 g was spread on an aluminum plate and degassed with a vacuum heating apparatus at 170 ° C. for 1 hour 30 minutes. Then, this was heated up to 190 degreeC, and also heat-cured by heat-retaining at 190 degreeC for 4 hours, and the brown benzoxazine resin hardened | cured material was obtained. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain a 109 μm flake, and the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 1.21 × 10 −7 m 2 / s.
Example 4
1- (3,4-Dihydro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1) obtained in Example 2 , 3-Benzoxazin-6-yl) cyclohexene was spread on an aluminum plate and degassed with a vacuum heating apparatus at 150 ° C. for 1 hour. Thereafter, this was heated from 150 ° C. to 250 ° C. over 2 hours, and further heated and cured at 250 ° C. for 1 hour to obtain a brown benzoxazine resin cured product. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain a 100 μm flake, and the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 1.26 × 10 −7 m 2 / s.
Comparative Example 1
2,5-bis (3,4-dihydro-3-phenyl-1,3-benzoxazine) propane (1.55 g) was spread on an aluminum plate and deaerated at 150 ° C. for 1 hour and 30 minutes using a vacuum heating apparatus. Thereafter, this was heated from 150 ° C. to 250 ° C. over 2 hours, and further heated and cured at 250 ° C. for 1 hour to obtain a brown benzoxazine resin cured product. The surface of the obtained cured product was polished with sandpaper (# 1200 and # 2000) to obtain 131 μm flakes, and then the thermal diffusivity was measured by the TWA method. As a result, the thermal diffusivity of the cured product was 0.99 × 10 −7 m 2 / s.
本発明によれば、より高い熱伝導率を有するベンゾオキサジン樹脂硬化物を製造提供することが可能である。
本発明によれば、より高い熱伝導率を有するベンゾオキサジン樹脂硬化物を製造するために用いられる原料となるベンゾオキサジン化合物およびその製造方法を提供することが可能である。当該ベンゾオキサジン樹脂硬化物は、放熱性を必要とする絶縁材料として有用である。 According to the present invention, it is possible to manufacture and provide a cured benzoxazine resin having a higher thermal conductivity.
ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened | cured material which has higher thermal conductivity, and its manufacturing method. The cured benzoxazine resin is useful as an insulating material that requires heat dissipation.
本発明によれば、より高い熱伝導率を有するベンゾオキサジン樹脂硬化物を製造するために用いられる原料となるベンゾオキサジン化合物およびその製造方法を提供することが可能である。当該ベンゾオキサジン樹脂硬化物は、放熱性を必要とする絶縁材料として有用である。 According to the present invention, it is possible to manufacture and provide a cured benzoxazine resin having a higher thermal conductivity.
ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the benzoxazine compound used as the raw material used in order to manufacture the benzoxazine resin hardened | cured material which has higher thermal conductivity, and its manufacturing method. The cured benzoxazine resin is useful as an insulating material that requires heat dissipation.
Claims (6)
- 式（１）
（式中、Ｘは式（Ａ−１）、式（Ａ−２）または式（Ａ−３）
で示される基を表わす。
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物。 Formula (1)
(In the formula, X represents the formula (A-1), the formula (A-2) or the formula (A-3).
Represents a group represented by
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by: - 式（１）で示されるベンゾオキサジン化合物であって、Ｘが式（Ａ−１）または式（Ａ−２）で示される基であることを特徴とする請求項１記載のベンゾオキサジン化合物。 The benzoxazine compound according to claim 1, which is a benzoxazine compound represented by the formula (1), wherein X is a group represented by the formula (A-1) or the formula (A-2).
- 式（２）
（式中、Ｒ５は、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される請求項１又は２記載のベンゾオキサジン化合物。 Formula (2)
(Wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound of Claim 1 or 2 shown by these. - 式（３）
（式中、Ｒ５は、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示される請求項１又は２記載のベンゾオキサジン化合物。 Formula (3)
(Wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
The benzoxazine compound of Claim 1 or 2 shown by these. - 請求項１乃至４のいずれかの請求項記載のベンゾオキサジン化合物を熱硬化させて得られるベンゾオキサジン樹脂硬化物。 A cured benzoxazine resin obtained by heat-curing the benzoxazine compound according to any one of claims 1 to 4.
- 式（１）
（式中、Ｘは下記（Ａ−１）、（Ａ−２）または（Ａ−３）
で示される基を表わす。
Ｒ１~Ｒ２５は、それぞれ独立して、水素原子、炭素数１~６のアルキル基、炭素数１~６のアルキルオキシ基、ハロゲン原子またはシアノ基を表わす。
Ｙ１およびＹ２は、それぞれ独立して、炭素数１~６のアルキル基、または、炭素数１~４のアルキル基で置換されてもよいフェニル基を表す。）
で示されるベンゾオキサジン化合物の製造方法であって、
式（４）
（式中、Ｒ１~Ｒ６およびＸは前記と同じ意味を表わす。）
で示されるビスフェノール化合物、式（５）
Ｙ１−ＮＨ２ （５）
（式中、Ｙ１は前記と同じ意味を表わす。）
で示される１級アミン化合物、
式（６）
Ｙ２−ＮＨ２ （６）
（式中、Ｙ２は前記と同じ意味を表わす）
で示される１級アミン化合物
およびホルムアルデヒドを、塩基の存在下に反応させる工程を含むことを特徴とする製造方法。 Formula (1)
(In the formula, X is the following (A-1), (A-2) or (A-3)
Represents a group represented by
R 1 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.
Y 1 and Y 2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. )
A process for producing a benzoxazine compound represented by:
Formula (4)
(Wherein R 1 to R 6 and X have the same meaning as described above.)
A bisphenol compound represented by formula (5)
Y 1 —NH 2 (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
Y 2 —NH 2 (6)
(Where Y 2 represents the same meaning as described above)
A process comprising reacting a primary amine compound represented by formula and formaldehyde in the presence of a base.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-201522 | 2011-09-15 | ||
| JP2011201522A JP2013060407A (en) | 2011-09-15 | 2011-09-15 | Benzoxazine compound and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013039185A1 true WO2013039185A1 (en) | 2013-03-21 |
Family
ID=47883402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/073558 WO2013039185A1 (en) | 2011-09-15 | 2012-09-07 | Benzoxazine compound and manufacturing method therefor |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2013060407A (en) |
| TW (1) | TW201323415A (en) |
| WO (1) | WO2013039185A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484519A (en) * | 2018-02-05 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of benzoxazine resin monomer and its preparation method and application based on Cortex Magnoliae Officinalis derivative |
| CN113150229A (en) * | 2021-04-12 | 2021-07-23 | 中北大学 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516194B (en) * | 2011-10-18 | 2014-08-13 | 广东生益科技股份有限公司 | Benzoxazine intermediate and its preparation method |
| PT3450499T (en) | 2016-04-28 | 2024-01-12 | Jxtg Nippon Oil & Energy Corp | Composition for curable resin, and cured product thereof |
| JP6849698B2 (en) | 2016-12-09 | 2021-03-24 | Ｅｎｅｏｓ株式会社 | Cured resin composition, cured product and curing method of the cured resin composition, and semiconductor device |
| WO2018181857A1 (en) | 2017-03-31 | 2018-10-04 | Ｊｘｔｇエネルギー株式会社 | Curable resin composition, cured product of said composition, method of producing said composition and said cured product, and semiconductor device |
| CN111278883B (en) | 2017-10-27 | 2022-12-30 | Jxtg能源株式会社 | Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device |
| CN111278882B (en) | 2017-10-27 | 2022-12-30 | Jxtg能源株式会社 | Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device |
| CN111278884B (en) | 2017-10-27 | 2022-12-30 | Jxtg能源株式会社 | Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device |
| US20220106437A1 (en) | 2018-12-10 | 2022-04-07 | Eneos Corporation | Composition for curable resin, cured product of said composition, production method for said composition and said cured product, and semiconductor device |
| JP7569784B2 (en) | 2019-04-26 | 2024-10-18 | 株式会社Ｅｎｅｏｓマテリアル | Composition for cured resin, cured product of said composition, methods for producing said composition and said cured product, and semiconductor device |
| JP2022013415A (en) * | 2020-07-03 | 2022-01-18 | Ｅｎｅｏｓ株式会社 | Method for Producing Mixture Containing Benzoxazine Compound |
| JP2022013410A (en) * | 2020-07-03 | 2022-01-18 | Ｅｎｅｏｓ株式会社 | Benzoxazine compound-containing mixture, curable composition containing the same, and cured product obtained by curing the curable composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171498A (en) * | 1997-05-01 | 1999-03-16 | Advanced Ceramics Corp | Composition for forming highly thermally conductive polybenzoxazine-based material and production thereof |
| JP2006306778A (en) * | 2005-04-28 | 2006-11-09 | Yokohama Rubber Co Ltd:The | New compound and curable resin composition using the same |
| WO2008123237A1 (en) * | 2007-03-26 | 2008-10-16 | Sumitomo Chemical Company, Limited | Epoxy resin composition |
-
2011
- 2011-09-15 JP JP2011201522A patent/JP2013060407A/en not_active Withdrawn
-
2012
- 2012-09-07 WO PCT/JP2012/073558 patent/WO2013039185A1/en active Application Filing
- 2012-09-12 TW TW101133307A patent/TW201323415A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171498A (en) * | 1997-05-01 | 1999-03-16 | Advanced Ceramics Corp | Composition for forming highly thermally conductive polybenzoxazine-based material and production thereof |
| JP2006306778A (en) * | 2005-04-28 | 2006-11-09 | Yokohama Rubber Co Ltd:The | New compound and curable resin composition using the same |
| WO2008123237A1 (en) * | 2007-03-26 | 2008-10-16 | Sumitomo Chemical Company, Limited | Epoxy resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484519A (en) * | 2018-02-05 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of benzoxazine resin monomer and its preparation method and application based on Cortex Magnoliae Officinalis derivative |
| CN108484519B (en) * | 2018-02-05 | 2019-12-03 | 中国科学院宁波材料技术与工程研究所 | A kind of benzoxazine resin monomer and its preparation method and application based on Cortex Magnoliae Officinalis derivative |
| CN113150229A (en) * | 2021-04-12 | 2021-07-23 | 中北大学 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
| CN113150229B (en) * | 2021-04-12 | 2022-07-05 | 中北大学 | High-carbon-residue fluorine-containing pyridine type benzoxazine resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013060407A (en) | 2013-04-04 |
| TW201323415A (en) | 2013-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013039185A1 (en) | Benzoxazine compound and manufacturing method therefor | |
| CN101993407B (en) | Indoline compound for preparing silodosin and preparation method thereof | |
| JP5187616B2 (en) | Process for producing β-nitrostyrene compound | |
| CN115340539A (en) | Process for preparing finerenone and intermediates thereof | |
| JP6612078B2 (en) | Benzoxazine compound, method for producing the same, and benzoxazine resin | |
| CN111944539B (en) | Fluropiperazine-based benzoxazole liquid crystal compound and preparation method thereof | |
| JPWO2017164260A1 (en) | Benzoxazine compound, method for producing the same and benzoxazine resin | |
| TWI745452B (en) | Naphthobischalcogenadiazole derivatives and method for producing the same | |
| JP2008540526A (en) | Bisamination of aryl halides | |
| JP2002212181A (en) | Method for producing benzazole group-containing triazine compound | |
| JP2015203040A (en) | Compound and cured product | |
| JP2019522662A (en) | New method for producing Vemurafenib | |
| KR101995655B1 (en) | Aromatic diamines and intermediates thereof, and process for their preparation | |
| JP7079863B2 (en) | New benzoxazine compound | |
| JP2015155385A (en) | Tetracarboxylic acid dianhydride, polyamic acid and polyimide having fluorene skeleton | |
| JPWO2011158813A1 (en) | Process for producing N-substituted-2-amino-4- (hydroxymethylphosphinyl) -2-butenoic acid | |
| JP6603043B2 (en) | Aromatic diamines and intermediates thereof, and methods for producing them | |
| JP5870114B2 (en) | Enantiomerically pure binaphthol derivative and method for producing the same (ENANTIOMERICALLY PURE BINAPHTOL DERIVATEIVES AND METHOD FOR PREPARING THE SAE) | |
| TWI406859B (en) | Pentaphenyldiamine-containing bismaleimide compound and producing method thereof | |
| JP4144223B2 (en) | Method for producing chromone derivative | |
| JP2016193842A (en) | Benzooxazole-2-yl-diphenylether having amino group and/or nitro group and derivative thereof, and method for producing the same | |
| JP4531610B2 (en) | Method for producing croconic acid or a salt thereof | |
| JP2009191014A (en) | Method for producing aminoarylaminoarazole | |
| KR101995656B1 (en) | Aromatic diamines and intermediates thereof, and process for their preparation | |
| JP2021524500A (en) | A novel method for producing a diaminopyrimidine derivative or an acid addition salt thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12831628 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12831628 Country of ref document: EP Kind code of ref document: A1 |