JP2013060407A - Benzoxazine compound and method for producing the same - Google Patents
Benzoxazine compound and method for producing the same Download PDFInfo
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- JP2013060407A JP2013060407A JP2011201522A JP2011201522A JP2013060407A JP 2013060407 A JP2013060407 A JP 2013060407A JP 2011201522 A JP2011201522 A JP 2011201522A JP 2011201522 A JP2011201522 A JP 2011201522A JP 2013060407 A JP2013060407 A JP 2013060407A
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- 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
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- 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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- 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
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等に関する。 The present invention relates to a benzoxazine compound and a production method thereof.
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(例えば、特許文献1)。 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 to form benzo It is known to produce a cured oxazine resin (for example, Patent Document 1).
本発明の目的は、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等を提供することである。 The objective of this invention is providing the benzoxazine compound used as a raw material used in order to manufacture the benzoxazine resin hardened | cured material which has higher thermal conductivity, its manufacturing method, etc.
このような状況下、本発明者らは鋭意検討した結果、以下の本発明に至った。
1.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(以下、本発明化合物と記すこともある);
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(A−1)または(A−2)であることを特徴とする前項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。)
で示されるベンゾオキサジン化合物;
5.前項1乃至3のいずれかの前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(以下、本発明樹脂硬化物と記すこともある。);
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(即ち、本発明化合物)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)
(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)
(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(以下、本発明製造方法と記すこともある。);
等を提供するものである。
Under such circumstances, the present inventors diligently studied, and as a result, reached the following present invention.
1. 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 represent 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by the following (hereinafter sometimes referred to as the present compound);
2. A benzoxazine compound represented by formula (1), wherein X is (A-1) or (A-2);
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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
5. A cured benzoxazine resin obtained by heat-curing the benzoxazine compound according to any one of the preceding items 1 to 3 (hereinafter sometimes referred to as the cured resin product of the present invention);
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 represent 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A process for producing a benzoxazine compound represented by the formula (ie, the compound of the present invention)
Formula (4)
(In the formula, R 1 to R 6 and X have the same meaning as described above.)
A bisphenol compound represented by formula (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
(Where Y 2 represents the same meaning as described above)
A production method comprising the step of reacting a primary amine compound and formaldehyde represented by the above in the presence of a base (hereinafter sometimes referred to as the production method of the present invention);
Etc. are provided.
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等を提供することが可能である。 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, its manufacturing method, etc.
以下、本発明を詳細に説明する。
本発明化合物は、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である。
Hereinafter, the present invention will be described in detail.
The compound of the present invention has the 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 represent 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
It is a benzoxazine compound shown by.
式(1)における好ましいXとしては、例えば、(A−1)または(A−2)で示される基を挙げることができる。 As preferable X in Formula (1), group shown by (A-1) or (A-2) can be mentioned, for example.
式(1)における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、シアノ基である。
ここで「炭素数1〜6のアルキル基」としては、例えば、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、シクロヘキシル基等を挙げることができる。また「炭素数1〜6のアルキルオキシ基」としては、例えば、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、シクロヘキシルオキシ基等を挙げることができる。また「ハロゲン原子」としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等を挙げることができる。
R 1 to R 25 in Formula (1) are each independently 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.
Examples of the “alkyl group having 1 to 6 carbon atoms” include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Examples of the “C 1-6 alkyloxy group” include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, n-hexyloxy group, cyclohexyloxy group and the like. Can do. Examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
式(1)におけるY1およびY2は、それぞれ独立して、例えば、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いてもよいフェニル基である。
ここで「炭素数1〜6のアルキル基」としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n−ブチル基、t−ブチル基、n−ヘキシル基、シクロヘキシル基等を挙げることができる。また「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、例えば、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、4−t−ブチルフェニル基等を挙げることができる。
Y 1 and Y 2 in Formula (1) are each independently a phenyl group which may be substituted with, for example, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
Here, examples of the “alkyl group having 1 to 6 carbon atoms” include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group and the like. Can be mentioned. Examples of the “phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms” include, for example, a phenyl group, o-toluyl group, m-toluyl group, p-toluyl group, 4-isopropylphenyl group, 4- Examples thereof include a t-butylphenyl group.
本発明化合物としては、具体的には例えば、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−メチルー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)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、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)シクロヘキサン等を挙げることができる。 Specific 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-benzoxazine- 6-yl) benzene, 1- (3,4 Dihydro-8-t-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-benzoxazine-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-me Ru-3- (3-toluyl) -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-benzoxazin-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-dihydro-3- (4-t-butylphenyl) -1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3,8-dimethyl-1,3- Benzoxazin-6-yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-ethyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-isopropyl Ro 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 Benzoxazin-6-yl) -4- (3,4-dihydro-3-tert-butyl-1,3-benzoxazin-6-yl) benzene, 1- (3,4-dihydro-3-cyclohexyl luo 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-benzoxazine-6 -Ill)- -(3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-isopropyl-3-phenyl-1,3-benzoxazine-6 -Yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-t-butyl-3-phenyl-1 , 3-Benzoxazin-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-jihi Dro-8-methyl-3-phenyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-8-methyl-3- (4-toluyl) -1,3-benzoxazine- 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-benzoxazin-6-yl) cyclohexene, -(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) cyclohexene, 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) cyclohexene, 1- (3,4-dihydro-3,8-dimethyl-1, 3-Benzoxazin-6-yl) -4- (3,4-dihydro-3-methyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-ethyl-8- Methyl-1,3-benzooxy Gin-6-yl) -4- (3,4-dihydro-3-ethyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-isopropyl-8-methyl- 1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-isopropyl-1,3-benzoxazin-6-yl) cyclohexene, 1- (3,4-dihydro-3-t -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 lu 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-benzo Oxazin-6-yl) -4- (3,4-dihydro-3-phenyl-1,3-benzoxazin-6-yl) cyclohexane, 1- (3,4-dihydro-8-ethyl-3-phenyl- 1,3-benzoxazin-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-phenyl-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- -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-benzooxy Sadin-6-yl) -4- (3,4-dihydro-3- (4-tert-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 -Dihydro-3-t-butyl-8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-t-butyl-1,3-benzoxazin-6-yl) Cyclohexane, 1- (3,4-dihydro-3-cyclohexyl-u 8-methyl-1,3-benzoxazin-6-yl) -4- (3,4-dihydro-3-cyclohexyl-1,3-benzoxazine -6-yl) cyclohexane and the like.
本発明化合物は、例えば、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)
(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)
(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(即ち、本発明製造方法)により製造することができる。
The compound of the present invention is represented, for example, by the formula (4)
(In the formula, 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)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
(Where Y 2 represents the same meaning as described above)
It can manufacture by the manufacturing method (namely, this invention manufacturing method) including the process with which the primary amine compound and formaldehyde which are shown by these are made to react in presence of a base.
本発明製造方法に用いられる「ビスフェノール化合物(4)」としては、例えば、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、1,4−ビス(3−メチルー4−ヒドロキシフェニル)シクロヘキサン等を挙げることができる。 Examples of the “bisphenol compound (4)” used in the production method of the present invention include 1,4-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) cyclohexene, and 1,4-bis. (4-hydroxyphenyl) cyclohexane, 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxy Phenyl) 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-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-isopropyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3- Isopropyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-isopropyl4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-t-butyl 4-hydroxy Phenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-tert-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-tert-butyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-cyclohexyl 4- Droxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexene, 1- (3-cyclohexyl 4-hydroxyphenyl) -4 -(4-hydroxyphenyl) cyclohexane, 1,4-bis (3-methyl-4-hydroxyphenyl) benzene, 1,4-bis (3-methyl-4-hydroxyphenyl) cyclohexene, 1,4-bis (3-methyl-) 4-hydroxyphenyl) cyclohexane and the like.
上記のビスフェノール化合物(4)は、例えば、特開2002−308808号公報、特開2002−308809号公報、特開2002−363117等に記載される公知の方法およびそれに準じた方法により製造することができる。 Said bisphenol compound (4) can be manufactured by the well-known method described in Unexamined-Japanese-Patent No. 2002-308808, Unexamined-Japanese-Patent No. 2002-308809, Unexamined-Japanese-Patent No. 2002-363117, etc., and the method according to it, for example. it can.
本発明製造方法に用いられる「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」としては、例えば、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、4−t−ブチルアニリン等を挙げることができる。
1級アミン化合物の使用量としては、ビスフェノール化合物(5)1モルに対して、
例えば、1モル〜20モルの範囲を挙げることができる。好ましくは、例えば、1.5モル〜10モルの範囲が挙げられる。より好ましくは、例えば、1.8モル〜5モルの範囲を挙げることができる。
Examples of the “primary amine compound represented by the formula (5)” and the “primary amine compound represented by the formula (6)” used in the production method of the present invention include methylamine, ethylamine, n-propylamine, and isopropyl. Examples include amine, n-butylamine, t-butylamine, n-hexylamine, cyclohexylamine, aniline, o-toluidine, m-toluidine, p-toluidine, 4-isopropylaniline, 4-t-butylaniline and the like.
The amount of the primary amine compound used is 1 mol of the bisphenol compound (5).
For example, the range of 1 mol-20 mol can be mentioned. Preferably, the range of 1.5 mol-10 mol is mentioned, for example. More preferably, the range of 1.8 mol-5 mol can be mentioned, for example.
本発明製造方法に用いられる「ホルムアルデヒド」としては、例えば、ホルムアルデヒド水溶液、1,3,5−トリオキサン、パラホルムアルデヒド等を挙げることができる。
ホルムアルデヒドの使用量としては、ビスフェノール化合物(4)1モルに対して、例えば、2モル〜100モルの範囲を挙げることができる。好ましくは、例えば、3モル〜20モルの範囲が挙げられる。より好ましくは、例えば、3.5モル〜10モルの範囲を挙げることができる。
Examples of the “formaldehyde” used in the production method of the present invention include formaldehyde aqueous solution, 1,3,5-trioxane, paraformaldehyde and the like.
As usage-amount of formaldehyde, the range of 2 mol-100 mol can be mentioned with respect to 1 mol of bisphenol compounds (4), for example. Preferably, the range of 3 mol-20 mol is mentioned, for example. More preferably, the range of 3.5 mol-10 mol can be mentioned, for example.
本発明製造方法に用いられる「塩基」としては、例えば、水酸化ナトリウム、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、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、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、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、1,8-ジアザビシクロ〔5,4,0〕ウンデセ-7-エン等の2級アミン及び3級アミン;ピリジン、イミダゾール等の塩基性含窒素複素環化合物;等を挙げることができる。
塩基の使用量としては、例えば、ビスフェノール化合物(4)1モルに対して、例えば、0.001モル〜100モルの範囲を挙げることができる。好ましくは、例えば、0.005モル〜20モルの範囲が挙げられる。より好ましくは、例えば、0.01モル〜10モルの範囲が挙げられる。尚、塩基が反応条件下で液体である場合には、当該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。
Examples of the “base” used in the production method of the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; sodium carbonate, Alkali metal carbonates such as potassium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate and potassium bicarbonate; triethylamine, diisopropylethylamine, dipropylamine, dibutylamine, tributylamine, pyrrolidine, piperidine, diamylamine, dicyclohexylamine, tripropyl And secondary amines and tertiary amines such as amines and 1,8-diazabicyclo [5,4,0] undec-7-ene; basic nitrogen-containing heterocyclic compounds such as pyridine and imidazole; and the like.
As the usage-amount of a base, the range of 0.001 mol-100 mol can be mentioned with respect to 1 mol of bisphenol compounds (4), for example. Preferably, the range of 0.005 mol-20 mol is mentioned, for example. More preferably, the range of 0.01 mol-10 mol is mentioned, for example. In addition, when a base is a liquid under reaction conditions, you may use the said base as a solvent, and the usage-amount of the base in that case is not restrict | limited in particular.
本発明製造方法は、通常、溶媒の存在下実施される。尚、溶媒は、反応中、還流させておいてもよい。
本発明製造方法に用いられる「溶媒」としては、例えば、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、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、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、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、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、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、クロロベンゼン等のハロゲン化炭化水素溶媒;水;等を挙げることができる。
尚、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く、その場合の溶媒の使用量としては、特に制限されない。
The production method of the present invention is usually carried out in the presence of a solvent. The solvent may be refluxed during the reaction.
Examples of the “solvent” used in the production method of the present invention 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. Solvents; aliphatic hydrocarbon solvents such as toluene, xylene, benzene, etc .; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, dimethyl sulfoxide; acetonitrile, benzonitrile, etc. Examples thereof include nitrile solvents; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, and chlorobenzene; water;
In addition, you may use a solvent, mixing multiple types of solvent. Further, as described above, a base may be used as a solvent, and the amount of the solvent used in that case is not particularly limited.
本発明製造方法に含まれる工程における反応は、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、窒素ガスやアルゴンガス等の不活性ガス雰囲気下で行ってもよい。
反応温度としては、例えば、0℃〜150℃の範囲等を挙げることができる。好ましくは、例えば、20℃〜120℃の範囲等が挙げられる。より好ましくは、例えば、40℃〜100℃の範囲等を挙げることができる。
The reaction in the steps included in the production method of the present invention may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
As reaction temperature, the range of 0 degreeC-150 degreeC etc. can be mentioned, for example. Preferably, the range of 20 degreeC-120 degreeC etc. are mentioned, for example. More preferably, the range of 40 degreeC-100 degreeC etc. can be mentioned, for example.
本発明製造方法に含まれる工程における反応は、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。反応時間としては、例えば、1時間〜100時間の範囲内等を挙げることができる。 The reaction in the steps included in the production method of the present invention can be followed by measurement such as liquid chromatography. It is preferable to carry out the reaction until no increase in the compound of the present invention or a decrease in the bisphenol compound (4) is observed. Examples of the reaction time include a range of 1 hour to 100 hours.
本発明製造方法に含まれる工程における反応の終了後、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、本発明化合物を得ることができる。取り出された本発明化合物は、例えば、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。 After completion of the reaction in the steps included in the production method of the present invention, the compound of the present invention can be obtained by subjecting the obtained 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.
続いて、本発明樹脂硬化物について説明する。
本発明樹脂硬化物は、本発明化合物を熱硬化させて得られる。
本発明樹脂硬化物は、1種の本発明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。
本発明樹脂硬化物の製造方法としては、例えば、(a)所定の温度まで加熱して硬化させる方法、(b)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を挙げることができる。
Then, this invention resin hardened | cured material is demonstrated.
The cured resin of the present invention is obtained by thermally curing the compound of the present invention.
The cured resin product of the present invention may be a cured resin product obtained by curing one type of the present compound, or a cured resin product obtained by curing a mixture of two or more different types of the present compound. May be.
As a method for producing the cured resin of the present invention, for example, (a) a method of heating and curing to a predetermined temperature, (b) melting and pouring into a mold or the like, and further heating and molding the mold Examples thereof include (c) a method in which a melt of the compound of the present invention is injected into a preheated mold and cured.
以下、実施例により本発明を更に詳細に説明する。
尚、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。
Hereinafter, the present invention will be described in more detail with reference to examples.
The thermal diffusivity was measured by the TWA method (thermal diffusivity measuring device, Eye Phase Mobile, manufactured by Eye Phase Co., Ltd.).
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)
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 under reflux conditions for 23 hours. 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)
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)
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 37% formaldehyde aqueous solution was charged while keeping 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)
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%。
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%.
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。
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.
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。
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.
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。
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(即ち、本発明化合物)およびその製造方法等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(即ち、本発明樹脂硬化物)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 (namely, this invention compound) used as the raw material used in order to manufacture benzoxazine resin hardened | cured material which has higher thermal conductivity, its manufacturing method, etc. is there. The benzoxazine resin cured product (that is, the resin cured product of the present invention) is useful as an insulating material that requires heat dissipation.
Claims (6)
(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。 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 represent 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
(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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
(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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A benzoxazine compound represented by:
(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)
(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)
(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 represent 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 a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. )
A process for producing a benzoxazine compound represented by:
Formula (4)
(In the formula, R 1 to R 6 and X have the same meaning as described above.)
A bisphenol compound represented by formula (5)
(In the formula, Y 1 represents the same meaning as described above.)
A primary amine compound represented by:
Formula (6)
(Where Y 2 represents the same meaning as described above)
The manufacturing method characterized by including the process of making the primary amine compound and formaldehyde shown by presence of a base react.
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