WO2015125734A1 - Dérivé d'acide halohexahydrophtalique - Google Patents

Dérivé d'acide halohexahydrophtalique Download PDF

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Publication number
WO2015125734A1
WO2015125734A1 PCT/JP2015/054141 JP2015054141W WO2015125734A1 WO 2015125734 A1 WO2015125734 A1 WO 2015125734A1 JP 2015054141 W JP2015054141 W JP 2015054141W WO 2015125734 A1 WO2015125734 A1 WO 2015125734A1
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halohexahydrophthalic
general formula
acid derivative
atom
represented
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PCT/JP2015/054141
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English (en)
Japanese (ja)
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進介 井上
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マナック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3

Definitions

  • the present invention relates to a halohexahydrophthalic acid derivative and a method for producing the same.
  • Polyimide has excellent heat resistance, chemical resistance, radiation resistance, electrical insulation, mechanical properties, etc., so flexible printed wiring circuit substrates, tape automation bonding substrates, semiconductor element protective films and interlayers Widely used in various electronic devices such as insulating films. Polyimide is also a very useful material in terms of simplicity of manufacturing method, high film purity, and ease of improving physical properties. In recent years, material design of functional polyimide suitable for various applications has been made. .
  • Typical examples of general-purpose polyimides include wholly aromatic polyimides obtained by polycondensation reaction of aromatic tetracarboxylic dianhydrides and aromatic diamines.
  • the wholly aromatic polyimide has excellent heat resistance, chemical resistance, etc., but it has a problem that it is inferior in transparency because it is colored deep yellow, and inferior in workability because it is insoluble in general organic solvents. is there.
  • an ester group-containing semi-alicyclic tetracarboxylic dianhydride has been reported as a raw material for polyimide having excellent heat resistance and high transparency (see, for example, Patent Document 1).
  • an alicyclic tetracarboxylic dianhydride that can be used as a raw material monomer for polyimide, which has no absorption in the ultraviolet region and has excellent light transmittance and high insulation, and further improved processability and excellent solubility in organic solvents.
  • the present invention is an alicyclic or semi-alicyclic tetracarboxylic dianhydride that can be a raw material monomer for polyimides that have improved transparency and processability as well as excellent properties of conventional polyimides such as heat resistance and chemical resistance. It is an object of the present invention to provide a halohexahydrophthalic acid derivative that is a synthetic intermediate of a product and a method for producing the same.
  • the present inventor paid attention to a compound having a hexahydrophthalic acid skeleton as an alicyclic or semi-alicyclic tetracarboxylic dianhydride that can be a raw material monomer of polyimide having such characteristics, and firstly, a synthetic intermediate thereof
  • a novel halohexahydrophthalic acid derivative and a method for producing the same were found, and the present invention was completed.
  • the present invention relates to the general formula (1): (In the formula, X represents a chlorine atom or a bromine atom, R 1 and R 2 each independently represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, or R 1 and R 2 are Together represent an oxygen atom) It is related with the halo hexahydrophthalic acid derivative shown by these.
  • the present invention also relates to a general formula (1): (In the formula, X represents a chlorine atom or a bromine atom, R 1 and R 2 each independently represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, or R 1 and R 2 are Together represent an oxygen atom)
  • a process for producing a halohexahydrophthalic acid derivative represented by a) 1,2,3,6-tetrahydrophthalic anhydride is reacted with a chlorinating reagent or brominating reagent to give a general formula (2): (Wherein X represents a chlorine atom or a bromine atom) And b) optionally subjecting the halohexahydrophthalic anhydride represented by the general formula (2) to hydrolysis or alcoholysis to give a general formula (2) 3): (Wherein X represents a chlorine atom or a bromine atom, and R 1a and R 2a each independently represents a hydroxy group or an alkoxy group having 1 to 4
  • the present invention provides a halohexahydrophthalic acid derivative that is a synthetic intermediate of an alicyclic or semi-alicyclic tetracarboxylic dianhydride that can be a raw material monomer for polyimide, and a method for producing the same.
  • the derivatives are industrially advantageous because they are readily available and can be produced from inexpensive reagents. Further, since the derivative has a halogen atom, it can be easily applied as a building block of an alicyclic or semi-alicyclic tetracarboxylic dianhydride.
  • An alicyclic or semi-alicyclic tetracarboxylic dianhydride is expected to impart flexibility to the resulting polyimide and improve processability and solubility in organic solvents. Further, since the conjugated system is interrupted by the saturated ring, it is expected to suppress the absorption in the ultraviolet region and improve the transparency.
  • Example 1 is a 1 H-NMR spectrum of the compound obtained in Example 1.
  • the halohexahydrophthalic acid derivative of the present invention has the general formula (1): (In the formula, X represents a chlorine atom or a bromine atom, R 1 and R 2 each independently represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, or R 1 and R 2 are Together represent an oxygen atom) Indicated by
  • the “alkoxy group having 1 to 4 carbon atoms” means that a monovalent group of a linear or branched aliphatic saturated hydrocarbon having 1 to 4 carbon atoms is an oxygen atom.
  • the halohexahydrophthalic acid derivative represented by the general formula (1) has the general formula (2): (Wherein X represents a chlorine atom or a bromine atom)
  • the halo hexahydrophthalic anhydride shown by these is included.
  • the halohexahydrophthalic anhydride represented by the general formula (2) corresponds to the case where R 1 and R 2 together represent an oxygen atom in the general formula (1).
  • the halohexahydrophthalic acid derivative represented by the general formula (1) has the general formula (3): (Wherein X represents a chlorine atom or a bromine atom, and R 1a and R 2a each independently represents a hydroxy group or an alkoxy group having 1 to 4 carbon atoms)
  • the ring-opened product shown by is included.
  • the ring-opened product represented by the general formula (3) corresponds to the case in which R 1 and R 2 each independently represent a hydroxy group or an alkoxy group having 1 to 4 carbon atoms in the general formula (1). .
  • the halohexahydrophthalic acid derivative represented by the general formula (1) includes halohexahydrophthalic anhydride and its ring-opened product.
  • the halohexahydrophthalic acid derivative represented by the general formula (1) may be a conformer or a mixture thereof.
  • the halohexahydrophthalic anhydride represented by the general formula (2) has the following formula: Axial form (axial form, a-form), Equatorial form (equatorial form, e-form) or a mixture thereof may be used.
  • halohexahydrophthalic acid derivative of the present invention can be produced according to the following scheme 1. (Wherein X, R 1a and R 2a have the same meanings as described above).
  • Step (a) is a method for preparing a halohexahydrophthalic anhydride represented by the general formula (2), wherein 1,2,3,6-tetrahydrophthalic anhydride represented by the formula (4) It reacts with a chlorinating reagent or a brominating reagent.
  • 1,2,3,6-tetrahydrophthalic anhydride represented by the formula (4) is a known compound, and can be obtained from a reagent supplier such as Wako Pure Chemical Industries, Ltd. Alternatively, it can be prepared from maleic anhydride and 1,3-butadiene according to the method described in Organic Syntheses, Coll. Vol. 4, pp. 890 (1963).
  • the chlorination reagent or bromination reagent is preferably a hydrogen chloride reagent or a hydrogen bromide reagent, respectively.
  • the hydrogen chloride reagent include hydrogen chloride gas or a non-aqueous solution of hydrogen chloride, such as a hydrogen chloride / methanol solution, a hydrogen chloride / dioxane solution, and a hydrogen chloride / ethyl acetate solution.
  • the hydrogen bromide reagent include hydrogen bromide gas or a non-aqueous solution of hydrogen bromide, such as a hydrogen bromide / ethanol solution, a hydrogen bromide / acetic acid solution, and the like.
  • the amount of the chlorinating reagent or brominating reagent is at least 1 mol, preferably 1 to 10 mol, relative to 1,2,3,6-tetrahydrophthalic anhydride (mol) represented by the formula (4). More preferably, it is 1 to 5 mol.
  • the reaction in the above step (a) can be carried out in the presence or absence of a solvent, preferably in the presence of a solvent.
  • the solvent that can be used is not particularly limited as long as it is inert to the reaction, and is appropriately selected depending on the desired reaction temperature. You may use individually or in mixture of 2 or more types of solvents in arbitrary ratios. Examples of such solvents include: alkanoic acids such as formic acid, acetic acid, propionic acid, butyric acid and isobutyric acid; cycloaliphatic hydrocarbons such as cyclohexane; halogenated aliphatic carbonization such as methylene chloride, carbon tetrachloride and ethylene dichloride.
  • Ether solvents such as diethyl ether, tetrahydrofuran, dioxane and the like can be mentioned.
  • alkanoic acids such as formic acid and acetic acid
  • ether solvents such as dioxane.
  • the reaction in the above step (a) is carried out at 0 ° C. to reflux temperature, preferably 0 ° C. to 80 ° C., more preferably room temperature (about 20 ° C.) to 60 ° C. for 1 minute to 24 hours, preferably 5 minutes to
  • the reaction can be carried out by reacting for 12 hours, more preferably 10 minutes to 6 hours.
  • the reaction mixture is subjected to an appropriate post-treatment operation known to those skilled in the art to obtain a halohexahydrophthalic anhydride represented by the general formula (2).
  • the halohexahydrophthalic anhydride represented by the general formula (2) may be subjected to further purification means known to those skilled in the art such as crystallization, recrystallization, column chromatography and the like. It may be purified as a conformer or as a mixture thereof.
  • Step (b) is a method for preparing a ring-opened product represented by the general formula (3), wherein the halohexahydrophthalic anhydride represented by the general formula (2) is subjected to hydrolysis or alcoholysis. It is what.
  • the hydrolysis reaction or alcohol decomposition reaction in the step (b) can be carried out by adding an acid or a base in the presence of water or alcohol, respectively.
  • the alcohol include alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, and t-butanol.
  • the acid include inorganic acids such as hydrochloric acid and sulfuric acid.
  • the base include inorganic bases such as sodium hydroxide and potassium hydroxide.
  • the amount of the acid or base is 0.01 to 20 moles, preferably 0.1 to 10 moles, more preferably 0.1 moles relative to the halohexahydrophthalic anhydride (mol) represented by the general formula (2). 5 to 5 moles.
  • the reaction in the above step (b) is carried out at 0 ° C. to reflux temperature, preferably 0 ° C. to 80 ° C., more preferably room temperature (about 20 ° C.) to 60 ° C. for 1 minute to 24 hours, preferably 5 minutes to
  • the reaction can be carried out by reacting for 12 hours, more preferably 10 minutes to 6 hours.
  • the reaction mixture is subjected to an appropriate post-treatment operation known to those skilled in the art to obtain a ring-opened product represented by the general formula (3).
  • the ring-opened product represented by the general formula (3) may be purified by further purification means known to those skilled in the art such as crystallization, recrystallization, column chromatography and the like.
  • Example 1 In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 152.15 g (1.0%) of cis-1,2,3,6-tetrahydrophthalic anhydride (THPD; manufactured by Wako Pure Chemical Industries, Ltd.) Mol) and 323.64 g of hydrogen bromide / acetic acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) (1.0 mol as pure hydrogen bromide) were added and reacted at 50 to 55 ° C. for 17 hours.
  • THPD cis-1,2,3,6-tetrahydrophthalic anhydride
  • the halohexahydrophthalic acid derivative of the present invention is industrially advantageous because it is easily available and can be produced from an inexpensive reagent. Further, since the derivative has a halogen atom, it can be easily applied as a building block of an alicyclic or semi-alicyclic tetracarboxylic dianhydride. An alicyclic or semi-alicyclic tetracarboxylic dianhydride is expected to impart flexibility to the resulting polyimide and improve processability and solubility in organic solvents. Further, since the conjugated system is interrupted by the saturated ring, it is expected to suppress the absorption in the ultraviolet region and improve the transparency.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne : un dérivé d'acide halohexahydrophtalique qui est un intermédiaire dans la synthèse du dianhydride d'acide tétracarboxylique alicyclique ou semi-alicyclique, et qui peut être utilisé en tant que monomère de départ pour obtenir un polyimide qui présente les excellentes caractéristiques inhérentes aux polyamides classiques, telles que la résistance à la chaleur et la résistance aux produits chimiques, et qui manifeste une transparence et une usinabilité améliorées ; et un procédé de production dudit dérivé d'acide halohexahydrophtalique.
PCT/JP2015/054141 2014-02-24 2015-02-16 Dérivé d'acide halohexahydrophtalique WO2015125734A1 (fr)

Priority Applications (1)

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JP2015536333A JPWO2015125734A1 (ja) 2014-02-24 2015-02-16 ハロヘキサヒドロフタル酸誘導体

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JP2014032479 2014-02-24
JP2014-032479 2014-02-24

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2530147A (en) * 1947-03-27 1950-11-14 Frederick C Bersworth Alkylene polyamine derivatives
JPH11222484A (ja) * 1997-12-02 1999-08-17 Manac Inc オキシジフタル酸無水物の製造方法
JP2002020486A (ja) * 2000-07-04 2002-01-23 Manac Inc 新規なポリイミド及びその製造方法
JP2003073372A (ja) * 2001-08-30 2003-03-12 Manac Inc フェニルエチニルフタル酸無水物誘導体の製造方法
JP2007314435A (ja) * 2006-05-23 2007-12-06 Mitsubishi Chemicals Corp テトラカルボン酸類またはこれらから誘導されるポリエステルイミド及びその製造方法
WO2010013620A1 (fr) * 2008-07-31 2010-02-04 マナック株式会社 Procédé de fabrication d'un dérivé d'anhydride phtalique
JP2012224755A (ja) * 2011-04-20 2012-11-15 Hitachi Chemical Dupont Microsystems Ltd 高透明なポリイミド前駆体及びそれを用いた樹脂組成物、ポリイミド成形体とその製造方法、プラスチック基板、保護膜とそれを有する電子部品、表示装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988302A (en) * 1974-05-24 1976-10-26 Texaco Development Corporation Polyurethanes prepared by reaction of organic polyisocyanate with brominated ester-containing polyols
JPH03215480A (ja) * 1990-01-12 1991-09-20 New Japan Chem Co Ltd １，２，３，６―テトラヒドロ無水フタル酸の製造法
JP5359029B2 (ja) * 2007-06-06 2013-12-04 Ｊｎｃ株式会社 酸二無水物、液晶配向膜および液晶表示素子

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2530147A (en) * 1947-03-27 1950-11-14 Frederick C Bersworth Alkylene polyamine derivatives
JPH11222484A (ja) * 1997-12-02 1999-08-17 Manac Inc オキシジフタル酸無水物の製造方法
JP2002020486A (ja) * 2000-07-04 2002-01-23 Manac Inc 新規なポリイミド及びその製造方法
JP2003073372A (ja) * 2001-08-30 2003-03-12 Manac Inc フェニルエチニルフタル酸無水物誘導体の製造方法
JP2007314435A (ja) * 2006-05-23 2007-12-06 Mitsubishi Chemicals Corp テトラカルボン酸類またはこれらから誘導されるポリエステルイミド及びその製造方法
WO2010013620A1 (fr) * 2008-07-31 2010-02-04 マナック株式会社 Procédé de fabrication d'un dérivé d'anhydride phtalique
JP2012224755A (ja) * 2011-04-20 2012-11-15 Hitachi Chemical Dupont Microsystems Ltd 高透明なポリイミド前駆体及びそれを用いた樹脂組成物、ポリイミド成形体とその製造方法、プラスチック基板、保護膜とそれを有する電子部品、表示装置

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TW201533016A (zh) 2015-09-01

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