KR101797794B1 - Process for producing trimellitic anhydride phenyl ester - Google Patents
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- KR101797794B1 KR101797794B1 KR1020137000323A KR20137000323A KR101797794B1 KR 101797794 B1 KR101797794 B1 KR 101797794B1 KR 1020137000323 A KR1020137000323 A KR 1020137000323A KR 20137000323 A KR20137000323 A KR 20137000323A KR 101797794 B1 KR101797794 B1 KR 101797794B1
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Abstract
An object of the present invention is to provide a process for efficiently producing anhydrous trimellitic acid phenyl ester at a high yield.
According to the present invention, in the production of anhydrous trimellitic acid phenyl ester by transesterification of carboxylic acid phenyl ester and anhydrous trimellitic acid, the reaction is carried out in the presence of a carboxylic acid alkali metal salt catalyst in an aromatic hydrocarbon solvent By weight of the trimellitic acid anhydride.
Description
The present invention relates to a process for producing anhydrous trimellitic acid phenyl esters.
The present invention also relates to a method for efficiently producing anhydrous trimellitic acid phenyl esters at a high yield.
The anhydrous trimellitic acid phenyl ester is useful as a raw material of a heat resistant resin such as a polyester imide resin, a curing agent or a modifier of an epoxy resin or a urethane resin, and particularly, a polyester imide resin Is expected to be used in flexible printed wiring boards and the like because it can impart low thermal expansion properties, heat resistance and flexibilizer characteristics in addition to low hygroscopicity and low water absorptivity depending on its structure. ) Phenyl esters are required.
Conventionally, several methods for producing trimellitic anhydride phenyl ester are known. For example, there is known a method of reacting anhydrous trimellitic acid halide with a bivalent aromatic diol in a mixed solvent of an aliphatic ketone and an aromatic hydrocarbon in the presence of an amine (Patent Document 1), and an anhydrous trimellitic acid halide And the resulting anhydrous trimellitic acid ester may contain a halogen-containing impurity derived from an acid halide, and there is a limitation in use depending on the use thereof. Further, a method of transesterifying an ester of an aromatic diol and anhydrous trimellitic acid is known.
For example, a method of transesterifying acetic acid ester of phenols with trimellitic anhydride in the presence of an phase transfer catalyst (Patent Document 2) is known, but the reaction selectivity is not sufficient.
There is also known a method in which acetic acid ester of phenols and trimellitic anhydride are subjected to transesterification reaction in the presence of a silica-alumina catalyst or an inorganic compound catalyst composed of an alkali metal or alkaline earth metal (patent document 3), and alkali metals and alkaline earth metals The inorganic compound to be a metal is insufficient in reaction selectivity, and the silica / alumina catalyst has insufficient reaction selectivity, and the catalyst itself is expensive.
Further, there is known a method in which an ester exchange reaction is carried out in the absence of a catalyst in a solvent such as triethyl biphenyl or diphenyl ether (Patent Document 4) in which a lower alocalic acid ester of an aromatic diol and anhydrous trimellitic acid are reacted (Patent Document 4) Reaction selectivity is also insufficient.
Further, a method of transesterifying acetic acid esters of phenols and trimellitic anhydride in the presence of a sodium acetate catalyst without using a solvent (Patent Document 5) is known, but the reaction selectivity is not sufficient.
Accordingly, in view of the above-mentioned situation in the production process by the transesterification reaction of anhydrous trimellitic acid ester, the present invention relates to a process for transesterifying a carboxylic acid phenyl ester and anhydrous trimellitic acid, The present invention also provides a method for producing an objective anhydrous trimellitic acid phenyl ester at a high selectivity and a high yield under conditions that are easy to carry out.
Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that, in a process for producing a carboxylic acid phenyl ester and an anhydrous trimellitic acid by using an ester exchange reaction as a raw material, an alkali metal carboxylate is used as a catalyst , And an aromatic transesterification reaction are carried out in an aromatic hydrocarbon solvent, an intended transesterification reaction proceeds selectively to obtain an aimed trimellitic anhydride phenyl ester at a high selectivity and a high yield, thereby completing the present invention.
That is, according to the present invention, in the production of anhydrous trimellitic acid phenyl ester by transesterification of a carboxylic acid phenyl ester with an anhydrous trimellitic acid, the reaction is carried out in an aromatic hydrocarbon solvent in the presence of a carboxylic acid alkali metal salt catalyst Wherein the amount of the trimellitic anhydride is less than the amount of the trimellitic anhydride.
According to the process for producing anhydrous trimellitic acid phenyl ester of the present invention, when the carboxylic acid phenyl ester and the anhydrous trimellitic acid are subjected to transesterification reaction, an alkali metal carboxylate salt is used as a catalyst and the reaction is carried out in an aromatic hydrocarbon solvent , The reaction selectivity is greatly improved as compared with the conventionally known ester exchange reaction in the production of trimellitic anhydride phenyl ester. As a result, the yield of the desired product is remarkably improved, and industrially, .
Since the production method of the present invention has a good selectivity of the desired esterification reaction, production of a high molecular weight (oligomer), which is difficult to remove by post treatment such as crystallization, is suppressed. As a result, Can be relatively easily obtained.
Further, in the transesterification reaction according to the production method of the present invention, even when a relatively large amount of mono-anhydrous trimellitic acid ester is produced as a target in the case of the di-anhydride trimellitic acid ester, , And the mono-anhydrous trimellitic acid ester is a precursor of the di-anhydride trimellitic acid ester. Therefore, when it is separated and recovered, it can be reused as a raw material of the desired diester.
In addition, since no acid chloride is used, it does not contain any halogen impurities derived from the influential acid chloride depending on the application.
The process for producing anhydrous trimellitic acid phenyl ester of the present invention is characterized in that, in the transesterification reaction between carboxylic acid phenyl ester and anhydrous trimellitic acid, an alkali metal carboxylate is used as a catalyst and the reaction is carried out in an aromatic hydrogen carbonate solvent .
In the above production process, the objective trimellitic anhydride phenyl ester is represented by the following general formula (1).
(Wherein A represents a residue obtained by removing a hydroxyl group from a mononuclear or polynuclear phenol of n-valence, R 4 represents an alkyl group, an alkoxyl group or a phenyl group, d represents 0 or an integer of 1 to 3, and n represents an integer of 1 to 4 Represents an integer.)
In the formula, A represents a residue obtained by removing a hydroxyl group from a mononuclear or polynuclear phenol of n-valent, specifically, A represents a residue of a mononuclear or polynuclear phenyl nucleus formed by removing n phenolic hydroxyl groups from a mononuclear or polynuclear phenol. Preferably, A is a monovalent monovinyl residue, a bivalent to tetravalent biphenyl or biphenyl residue, a trivalent trisphenyl residue or a tetravalent tetrakisphenyl residue. Particularly preferred A is a divalent monophenyl residue, a biphenyl residue, or a biphenyl residue.
In the formula, the alkyl group represented by R 4 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms A straight chain or branched chain alkyl group of 5 to 6 carbon atoms and a cycloalkyl group of 5 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, isobutyl, cyclohexyl, cyclopentyl and the like. These may have a substituent such as a phenyl group, an alkoxyl group, a halogen atom and an oxygen atom (cyclic ether group). In the formula, the phenyl group represented by R 4 may also have an alkyl group having 1 to 4 carbon atoms and / The alkoxy group may be substituted by 1 to 3 substituents.
In the formula, the alkoxyl group represented by R 4 is preferably a linear or branched alkoxyl group having 1 to 10 carbon atoms or a cyclic alkoxyl group having 5 to 10 carbon atoms, more preferably a carbon atom number A linear or branched alkoxy group having 1 to 4 carbon atoms, or a cycloalkoxy group having 5 to 6 carbon atoms. Specific examples include methoxy, ethoxy, isopropyloxy, cyclohexyloxy, cyclopentyloxy and the like. These may have a substituent such as a phenyl group, an alkoxyl group, a halogen atom or an oxygen atom (cyclic ether group).
In the production process of the present invention, the carboxylic acid phenyl ester which is a raw material of the trimellitic anhydride phenyl ester is not particularly limited as long as it has a carboxylic acid ester group capable of transesterification with anhydrous trimellitic acids by the production method of the present invention, Is not particularly limited, but is represented by, for example, the following formula (2).
(Wherein A and n are the same as those in formula (1), and R 3 represents a hydrogen atom, a saturated hydrocarbon group or a phenyl group.)
In the formula, the saturated hydrocarbon group represented by R 3 is a linear, branched or cyclic saturated hydrocarbon group, and the saturated hydrocarbon group may be substituted with a phenyl group or an alkoxyl group such as methoxy And may have an ether group.
The number of carbon atoms in the straight-chain or branched-chain saturated hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 4, and the number of carbon atoms in the cyclic saturated hydrocarbon group is preferably from 5 to 10, Preferred examples thereof include linear, branched or cyclic primary or secondary alkyl groups. Specific examples thereof include methyl, ethyl, propyl, n-butyl, t-butyl, And the like. The phenyl group may be substituted with an alkyl group or an alkoxyl group. However, since R 3 As, to exit generating a carboxylic acid (R 3 COOH) carboxyl group is bonded to R 3, anhydrous trimellitic acid than the boiling point of the low to the operation of the reaction preferably being in the transesterification reaction, R 3 Examples An excessively large number of carbon atoms is not desirable.
Such a carboxylic acid phenyl ester is not particularly limited and may be produced by a conventionally known method such as a method of converting a carboxylic acid ester such as acetic acid into an excess amount of a carboxylic anhydride such as anhydrous acetic acid, A method of reacting a carboxylic acid or a halogenated acyl in the presence of an esterification catalyst such as sulfuric acid, p-toluenesulfonic acid or the like can be used.
Specifically, for example, compounds represented by the following formulas 3 to 5
[Chemical Formula 3]
(In the formula, R 3 is the same as that of the formula (2), and Y represents a halogen atom.)
Carboxylic acid anhydride, carboxylic acid or halogenated acyl, and aromatic hydroxycarboxylic acid represented by the formula (6) as raw materials and can be obtained by a known esterification method.
(Wherein A and n are the same as those in formula (1)).
Examples of the aromatic hydroxides represented by the formula (6) include monophenyls having a substitution number n of 1 to 3 in the hydroxy group, biphenyls or biphenyls having 2 to 4 ns, tris Phenyls, tetrakisphenyls in which n is 4, and among them, monophenyls having n = 2 and biphenyls or biphenyls having 2 to 4 of n are preferable. Of these, monophenyls, biphenyls or biphenyls, in other words benzene diols, bisphenols or non-phenols, in which n is 2, are particularly preferred and they are represented by the following general formula (7).
(Formula of, R 1 and R 2 are each alkyl group independently represents an alkoxy group, an aromatic hydrocarbon group, a halogen, a, b are each independently 0 or an integer of 1 ~ 4, c is from 0 to 1 And X represents a single bond or a divalent linking group.)
In the above formula, the alkyl group represented by R 1 and R 2 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms, A linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, isobutyl, Hexyl, or cyclopentyl. These alkyl groups may have a substituent such as a phenyl group, an alkoxyl group, a halogen atom, or an oxygen atom (cyclic ether group).
The alkoxyl group is preferably a linear or branched alkoxyl group having 1 to 10 carbon atoms or a cyclic alkoxyl group having 5 to 10 carbon atoms, more preferably a linear or branched group having 1 to 4 carbon atoms Chain alkyl group and a cycloalkyl group having 5 to 10 carbon atoms. Specific examples thereof include methoxy, ethoxy, isopropyloxy, cyclohexyloxy, cyclopentyloxy and the like. These alkoxyl groups may have a substituent such as a phenyl group, an alkoxyl group, a halogen atom, or an oxygen atom (cyclic ether group).
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms such as phenyl group, naphthyl group and phenyloxy group. These aromatic hydrocarbon groups may have a substituent such as an alkyl group, an alkoxyl group or a halogen group.
The halogen group is preferably chlorine, bromine, or fluorine.
When a is 2 or more, R 1 may be the same or different, and when b is 2 or more, R 2 may be the same or different.
When c is 0, 1,4-position or 1,3-position is preferable, and when c is 1, 4,4'-position, 2,2'-position or 2,4'- Position is preferable, and the 4,4'-position is particularly preferable.
a and b each independently represent 0 or an integer of 1 to 4; Preferably 0 or 1 to 3, and particularly preferably 0, 1 or 2.
X represents a single bond or a divalent linking group. The preferable divalent linking group is an organic group and is specifically an oxygen atom (-O-), a sulfur atom (-S-), a sulfonyl group (-SO2-), a carbonyl group (-CO-) An aromatic hydrocarbon group or an alkenylene group to which an alkylene group may be bonded.
Examples of the alkylene group include linear, branched and cyclic alkylene groups. Specific examples thereof include 1,2-ethanediyl, 1,3-propanediyl, methylene, 1,1-ethanediyl, 2,2- Propanediyl, 1,1-cyclohexanediyl, or 1,4-cyclohexylene.
Alkylene groups such as 1,1-ethanediyl, 2,2-propanediyl and 1,1-cyclohexanediyl are represented by the following formulas.
[expression]
(Wherein R 5 and R 6 each independently represent a hydrogen atom or an alkyl group, and when both of them are an alkyl group, they may be bonded to each other to form a ring).
R 5 and R 6 are preferably an alkyl group. The alkyl group is the same as that of R 1 and R 2 , and an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and an isopropyl group is preferable.
It is preferable that either or both of R 5 and R 6 is a primary or secondary alkyl group.
Specific examples of the aromatic hydrocarbon group include 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 2,2'-biphenylene, and the like . These aromatic hydrocarbon groups may have substituents such as alkyl groups or alkoxyl groups. Specific examples of the aromatic hydrocarbon group to which the alkylene group may be bonded include 1,3-diisopropylbenzene-α, α'-diyl, 1,4-diisopropylbenzene-α, -Diyl, or 1,4-dimethylbenzene-α, α'-diyl. Specific examples of the alkenylene group include vinylene and the like.
Specific examples of the aromatic diols represented by the formula (7) include hydroquinone, resorcin, 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 3-methyl- 3-isopropyl-4,4'-dihydroxy-p-terphenyl, 3,5-dimethyl-4,4'- dihydroxy- 3 '' '-dimethyl-4,4' '-dihydroxy-p-quaterphenyl, 3,3' '-diisopropyl-4,4' Benzene, 1,3- bis {1- (4-hydroxyphenyl) -1-methylethyl} benzene, 1- (3-hydroxyphenyl) -4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene, 1- - Cyclo (3-methyl-4-hydroxyphenyl) -1,1'-bicyclohexane-3,3'-diene, 4,4'-bis 1, 1'-bicyclohexane-3,3'-diene, and the like.
Accordingly, the aromatic diol represented by the general formula (7) and the carboxylic acid phenyl ester represented by the general formula (2) obtained from the carboxylic acids of the general formulas (3) to (5) are represented by the following general formula (8).
(Wherein R 1 , R 2 , a, b, c and X are the same as those of the formula (7), and R 3 is the same as that of the formula (2)
The bonding position of the ester group (R 3 COO group) is the same as the bonding position of the hydroxyl group of formula (7). When c is 0, 1,4-position or 1,3-position is preferable. When c is 1, , 4'-position, 2,2'-position or 2,4'-position is preferred, and 4,4'-position is particularly preferred.
The anhydrous trimellitic acid is represented by, for example, the following formula (9).
(Wherein R 4 and d are the same as those in formula (1)).
In the formula (9), the alkyl, alkoxyl and phenyl groups represented by R 4 in the formula are specifically the same as the alkyl, alkoxyl and phenyl groups of R 4 in formula (1). Also, d is preferably zero. Therefore, preferred trimellitic anhydride acids represented by the general formula (9) are trimellitic anhydride (non-substituted).
Therefore, the trimellitic anhydride phenyl ester represented by the formula (1) obtained by the production method of the present invention from the carboxylic acid phenyl ester represented by the formula (8) and the anhydrous trimellitic acid represented by the formula (9) (10).
(Wherein R 1 , R 2 , a, b, c and X are the same as those in the formula (7), and R 4 and d are the same as those in the formula (1)
The bonding position of the trimellitic anhydride ester group (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy group) is the same as the bonding position of the hydroxyl group of the formula Is 0, the 1,4-position or the 1,3-position is preferable, and when c is 1, the 4,4'- position, the 2,2'-position or the 2,4'- '-Position is particularly preferred.
Specific examples of the anhydrous trimellitic acid phenyl ester, which is a target related to the production method of the present invention represented by the formula (10), include 1,4-bis (1,3-dioxo-1,3-di (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) benzene, 4,4 ' -Bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) biphenyl, 4,4'-bis (1,3-dioxo-1,3-dihydro Dimethylbenzyloxy) -3,3'-dimethylbiphenyl, bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) Phenyl} methane, 2,2-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} propane, 1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} ethane, 1,1-bis {4- (1,3- Isobenzofuran-5-ylcarbonyloxy) phenyl} cyclohexane, 1, Phenyl} -3,3,5-trimethylcyclohexane, 9,9-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) Dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} fluorene, 3-methyl-4,4'- 1,3-dihydroiso-benzofuran-5-ylcarbonyloxy) terphenyl, 3-isopropyl-4,4 & 5-ylcarbonyloxy) terphenyl, 3,5-dimethyl-4,4'-di (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) Phenyl, 3,3 '' -dimethyl-4,4 '' '- di (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) 1-methylethyl] benzene, 1- {4- (1, 2-dihydroxybenzoyl) , 3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) -3-methylphenyl} -4- {4- (1,3-dioxo-1,3-dihydroisobenzo Furan-5-ylcarbonyloxy) phenyl} -1-cyclohexene, 4,4 -Bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) -3-methylphenyl} -1,1'-bicyclohexane- - Dien and others.
In the process for producing anhydrous trimellitic acid phenyl ester according to the present invention, when carboxylic acid phenyl ester and anhydrous trimellitic acid are used as raw materials and an ester exchange reaction is carried out, an alkali metal carboxylate is used as a catalyst, The reaction is carried out in a solvent.
Examples of the alkali metal salt forming the carboxylic acid alkali metal salt used as the catalyst include a lithium salt, a sodium salt, a potassium salt, a rubidium salt and a cesium salt. The sodium salt, the lithium salt and the potassium salt are preferable for the reason that the reaction rate is high, and particularly, the sodium salt and the lithium salt are preferable.
Examples of the carboxylic acid forming the carboxylic acid alkali metal salt include aliphatic or aromatic monocarboxylic acids, dicarboxylic acids or polyvalent carboxylic acids. The preferable carboxylic acid component is a monocarboxylic acid or a dicarboxylic acid, particularly a monocarboxylic acid.
The preferred number of carbon atoms of the carboxylic acid (including carbon in the carboxyl group) is 1 to 30, more preferably 1 to 10, and particularly preferably 1 to 5.
Examples of the hydrocarbon group constituting the group in which the carboxyl group is removed from the carboxylic acid include linear, branched or cyclic saturated hydrocarbon groups, unsaturated hydrocarbon groups and aromatic hydrocarbon groups. The hydrocarbon groups include, for example, aliphatic groups and aromatic groups May have a substituent of
Therefore, specific examples of the carboxylic acid alkali metal salt include alkali metal salts such as formic acid, acetic acid, propionic acid, pentanoic acid, hexanoic acid, stearic acid or cyclohexanecarboxylic acid as the alkali metal salts of saturated aliphatic monocarboxylic acids An alkali metal salt such as acrylic acid or crotonic acid as the unsaturated aliphatic monocarboxylic acid alkali metal salt and an alkali metal salt such as an alkali metal salt such as oxalic acid, malonic acid, succinic acid, glutaric acid or adipic acid as the alkali metal salt of saturated aliphatic dicarboxylic acid An alkali metal salt such as maleic acid or fumaric acid as the alkali metal salt of an unsaturated aliphatic dicarboxylic acid, an alkali metal salt such as benzoic acid or naphthoic acid as the aromatic monocarboxylic acid alkali metal salt, an alkali metal salt such as an aromatic dicarboxylic acid alkali metal salt Include alkali metal salts such as phthalic acid and terephthalic acid. Among these, preferred is an alkali metal salt of a saturated aliphatic carboxylic acid, particularly an alkali metal salt of an aliphatic carboxylic acid having about 1 to 5 carbon atoms such as an alkali metal acetate salt or an alkali metal propionate salt.
The amount of the alkali metal carboxylate to be used in the production process of the present invention is preferably 0.005 to 10 mol%, more preferably 0.01 to 5 mol%, based on the ester group in the starting carboxylic acid phenyl ester, , More preferably in the range of 0.05 to 3 mol%, particularly preferably in the range of 0.1 to 2.5 mol%. Here, mol% is a value defined by mol% = (moles of catalyst / moles of ester group) x 100. The number of moles of the ester group is (the number of moles of the starting carboxylic acid phenyl ester and the number of ester groups in the molecule). Accordingly, the carboxylic acid phenyl ester represented by the general formula (8) is preferably used in an amount of 0.01 to 20 mol%, more preferably 0.02 to 10 mol%, still more preferably 0.1 to 6 mol% And particularly preferably 0.2 to 5 mol%.
In the production process of the present invention, a reaction solvent is used in the reaction and an aromatic hydrocarbon solvent is used as the solvent. The physical properties of the solvent preferably have a boiling point of 190 캜 or higher, more preferably 230 캜 or higher. The aromatic hydrocarbon solvent is preferably a polycyclic aromatic hydrocarbon solvent, a condensed cyclic aromatic hydrocarbon solvent, an aromatic ether solvent in which an ether group is directly bonded to an aromatic group, and an aromatic type heat medium (heat medium) For example, biphenyl or terphenyl as a polycyclic aromatic hydrocarbon solvent, diisopropyl naphthalene as a condensed cyclic aromatic hydrocarbon solvent, or diisopropyl naphthalene as a condensed cyclic aromatic hydrocarbon solvent, Substituted phenyl ether such as anisole, diphenyl ether, or di-p-tolyl ether as an aromatic ether solvent in which an ether group is directly bonded to an aromatic group, And an S-S series (manufactured by Shinnitetsu Kagaku Co., Ltd.).
More preferably, an aromatic hydrocarbon solvent having two or three benzene rings in the molecule such as substituted or unsubstituted diphenyl ethers, di (phenoxy) benzenes, biphenyls, terphenyls, etc., or an alkyl Substituted naphthalenes, and the like. The substituent of the aromatic hydrocarbon solvent is preferably an alkyl group such as methyl group or propyl group or an alkoxyl group such as methoxy group. The number of carbon atoms is preferably about 1 to 4, and the number of substitution is preferably about 1 to 3 .
The amount of the solvent to be used can not be uniformly determined depending on the solubility, melting point, substituent, structure and the like of the starting carboxylic acid phenyl ester, and is preferably from 0.5 to 40 wt% based on 1 part by weight of the carboxylic acid phenyl ester More preferably in the range of 1 to 20 parts by weight, particularly preferably in the range of 2 to 10 parts by weight. In the production method of the present invention, the transesterification reaction of the carboxylic acid phenyl ester and the anhydrous trimellitic acid is carried out by using the carboxylic acid alkali metal salt catalyst in the above-mentioned range of the addition, and conducting the reaction in the aromatic hydrocarbon solvent, The reason for this is unclear, but the selectivity of the target is improved and the production of by-products such as oligomers is suppressed, and a target of high purity can be easily obtained in high yield.
In the production process of the present invention, the amount of the trimellitic anhydride to be used is usually 1 molar or more, preferably 1 to 5 molar times, particularly preferably 1.3 to 5 molar equivalents, based on the ester group in the carboxylic acid phenyl ester. 1.7 mole ratio. Here, the molar ratio of the use of anhydrous trimellitic acid to the ester group is (number of moles of trimellitic anhydride / number of moles of ester group). Therefore, the amount of the trimellitic anhydride to be used is generally 2 molar or more, preferably 2 to 10 molar times, particularly preferably 2.6 to 3.4 molar times, relative to the dibasic carboxylic acid phenyl ester represented by the general formula (8) Range.
The transesterification reaction temperature is usually in the range of 100 to 300 ° C, preferably in the range of 150 to 270 ° C, more preferably in the range of 190 to 250 ° C, and particularly preferably in the range of 200 to 230 ° C.
In addition, since it is preferable to react while distilling out the generated carboxylic acid, it is preferable that the carboxylic acid produced by the transesterification reaction is a carboxylic acid having a boiling point lower than that of the raw trimellitic acid anhydride.
The reaction pressure may be atmospheric pressure, under pressure or under reduced pressure, but is preferably atmospheric pressure to reduced pressure. For example, the reaction pressure may be adjusted according to the boiling point of the produced carboxylic acid.
Depending on the combination of the reaction solvent and the carboxylic acid phenyl ester, there is a possibility that the reaction solvent may also be drained from the reaction liquid along with the outflow of the carboxylic acid. In this case, a solvent may be appropriately added to the reaction system.
Although the reaction method is not particularly limited, for example, the carboxylic acid phenyl ester, the anhydrous trimellitic acid, the carboxylic acid alkali metal salt and the solvent are added to a reaction vessel in an inert atmosphere, and the temperature is raised under stirring , And the reaction is completed while discharging the generated carboxylic acid. Further, after completion of the reaction, a known method may be used as a method for separating and purifying an object from the reaction solution. For example, the reaction liquid may be cooled as it is or cooled by adding a poor solvent (poor solvent), and the precipitated crystals may be separated by filtration to obtain a crude product or a high purity product. If necessary, high-purity products can be obtained by recrystallization and filtration.
It is also possible to obtain a high-purity product in which the amount of metal such as an inorganic salt is further reduced by, for example, filtering the inorganic salt by filtration, or washing with water, the solvent in which the object is dissolved before crystallization by the above purifying operation .
When contacted with water, even if some or all of the acid anhydride groups are opened to form a carboxylic acid, it can be returned to the object by heating or reacting with an acid anhydride such as acetic anhydride.
Example
(Reference Example 1)
675.0 g (6.6 mol) of anhydrous acetic acid and 342.0 g (1.5 mol) of 2,2-bis (4-hydroxyphenyl) propane were added to a 3 L four-necked flask equipped with a thermometer, reflux condenser and stirring wing, After raising the temperature to 130 ° C, the reaction was further carried out at the same temperature for 2.5 hours under stirring.
After completion of the reaction, 703 g of toluene was added and the mixture was cooled. Water was added, stirred and washed with water.
Thereafter, toluene was distilled off from the oil layer obtained by separating and removing the water layer, and then 937 g of heptane was added thereto, followed by crystallization and filtration to obtain 2,2-bis (4- Acetophenylphenyl) propane (hereinafter referred to as BPA-DA).
(Example 1)
A 300-ml four-necked flask equipped with a stirrer, a thermometer, a Dean Stark and a reflux condenser was purged with nitrogen, and 25.0 g (0.080 mol) of BPA-DA obtained in Reference Example 1, 46.2 g (0.241 mol) of anhydrous trimellitic acid, 0.25 g (4.7 mol% based on BPA-DA) and 54.5 g of diphenyl ether were added.
Thereafter, the temperature was raised to 210 캜 under an atmospheric nitrogen flow, and the reaction was carried out for 7 hours while maintaining the temperature at 210 캜 under stirring. The reaction was carried out with flowing out the generated acetic acid under a nitrogen atmosphere. The temperature was raised to 210 DEG C, and the reaction solution after 4 hours and 7 hours was collected and analyzed by GPC (gel permeation chromatography). Table 1 shows the results.
The reaction selectivity of 2,2-bis {4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl} propane, which is the target (diimine trimellitic acid ester) 96.7%.
(Comparative Example 1 and Comparative Example 2)
The reaction was carried out in the same manner as in Example 1 except that 54.5 g of each of the solvents listed in Table 1 was used instead of the diphenyl ether as the solvent of Example 1. Table 1 shows the results of GPC analysis of the reaction solution after raising the temperature to 210 DEG C after 4 hours and 7 hours.
(Comparative Example 3)
The reaction was carried out in the same manner as in Example 1 except that the diphenyl ether solvent of Example 1 was used without solvent. Table 1 shows the results of GPC analysis of the reaction solution after raising the temperature to 210 DEG C after 4 hours and 7 hours.
(Examples 2 to 4)
Except that the catalysts listed in Table 2 were used in place of lithium acetate in Example 1 in an amount of 4.7 mol% based on BPA-DA, respectively. Table 2 shows the results of GPC analysis of the reaction solution after 4 hours and 7 hours after the temperature was raised to 210 deg.
(Comparative Example 4)
The reaction was carried out in the same manner as in Example 1 except that the lithium acetate catalyst of Example 1 was not used and was carried out without catalyst. Table 2 shows the results of GPC analysis of the reaction solution after 4 hours and 7 hours after the temperature was raised to 210 deg.
(Comparative Example 5)
The reaction was carried out in the same manner as in Example 1 except that 0.25 g of potassium hydroxide was used instead of the lithium acetate catalyst of Example 1. After raising the temperature to 210 DEG C, the reaction solution was sampled after 4 hours and 7 hours, and analyzed by GPC.
※ The selectivity was calculated by the area percentage of GPC.
※ Monoester refers to a compound in which only one of the acetate moieties of diacetate is transesterified to give anhydrous trimellitic acid ester, and the reaction rate indicates the reaction rate of diacetate.
※ The selectivity was calculated by the area percentage of GPC.
※ Monoester refers to a compound in which only one of the acetate moieties of diacetate is transesterified to give anhydrous trimellitic acid ester, and the reaction rate indicates the reaction rate of diacetate.
(Examples 5 and 6)
Except that sodium acetate was used in an amount of 4.7 mol% based on BPA-DA instead of lithium acetate and 55 g of each of the solvents described in Table 3 was used instead of 54.5 g of diphenyl ether. Table 3 shows the results of GPC analysis of the reaction solution after 7 hours and 12 hours after the temperature was raised to 210 deg.
(Example 7)
Except that 21.6 g of 4,4'-di (acetoxy) biphenyl was used instead of BPA-DA, 0.2 g of sodium acetate instead of lithium acetate and 142.6 g of diphenyl ether were used and the reaction temperature was set to 230 캜 The reaction was carried out in the same manner as in Example 1. Table 3 shows the results of GPC analysis of the reaction solution after 7 hours and 12 hours after the temperature was raised to 230 deg.
The reaction selectivity of the target 4,4'-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) biphenyl was 98.4%.
※ Selectivity was calculated as the area percentage of GPC.
※ Monoester refers to a compound in which only one of the acetate moieties of diacetate is transesterified to give anhydrous trimellitic acid ester, and the reaction rate indicates the reaction rate of diacetate.
According to the results of the examples and comparative examples of Tables 1 to 3, the production of by-products such as oligomers was small in the example of the present invention by the method of the comparative example, and the reaction selectivity of the object was high.
Claims (1)
[Chemical Formula 8]
(Wherein R 1 and R 2 each independently represent an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen group, R 3 represents a hydrogen atom, a saturated hydrocarbon group or a phenyl group, a and b each independently represent 0 or 1 If 1-4 represents an integer, a is 2 or more of, R 1 is may be the or different in the same respectively, or more b is 2, R 2 is may be the same, each different, c represents an integer of 0 or 1, , And X represents a single bond or a divalent linking group.)
[Chemical Formula 9]
(In the formula, R 4 represents an alkyl group, an alkoxyl group or a phenyl group, and d represents 0 or an integer of 1 to 3.)
[Chemical formula 10]
(Wherein R 1 , R 2 , a, b, c and X are the same as those in the formula (8), and R 4 and d are the same as those in the formula (9)
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| PCT/JP2011/063891 WO2011158928A1 (en) | 2010-06-18 | 2011-06-17 | Process for producing trimellitic anhydride phenyl ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000186080A (en) | 1998-12-21 | 2000-07-04 | New Japan Chem Co Ltd | Production of high-purity hydroquinone bis(anhydrotrimellitate) |
| JP2000191590A (en) | 1998-12-24 | 2000-07-11 | Nof Corp | Production of (meth)acrylic acid phenyl ester |
| JP2006206486A (en) | 2005-01-27 | 2006-08-10 | Manac Inc | Method for producing ester group-containing acid dianhydride derivative |
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| US3784573A (en) * | 1970-08-13 | 1974-01-08 | Standard Oil Co | Catalysis of trans-acidolysis reaction |
| JPH0741472A (en) * | 1993-07-29 | 1995-02-10 | New Japan Chem Co Ltd | Production of acid anhydride of trimellitic ester of phenols |
| JPH10147582A (en) * | 1996-11-20 | 1998-06-02 | Kanegafuchi Chem Ind Co Ltd | Production of trimelltic enter anhydride |
| EP2383265B1 (en) * | 2008-12-22 | 2015-03-11 | Honshu Chemical Industry Co., Ltd. | Method for manufacturing trimellitic anhydride aryl ester |
| US9096566B2 (en) * | 2009-02-12 | 2015-08-04 | Honshu Chemical Industry Co., Ltd. | Ester group-containing tetracarboxylic acid dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000186080A (en) | 1998-12-21 | 2000-07-04 | New Japan Chem Co Ltd | Production of high-purity hydroquinone bis(anhydrotrimellitate) |
| JP2000191590A (en) | 1998-12-24 | 2000-07-11 | Nof Corp | Production of (meth)acrylic acid phenyl ester |
| JP2006206486A (en) | 2005-01-27 | 2006-08-10 | Manac Inc | Method for producing ester group-containing acid dianhydride derivative |
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