JP6890871B1 - Method for producing ester group-containing acid dianhydride derivative - Google Patents

Abstract

The present invention can avoid impurities that adversely affect the semiconductor element, and can efficiently use an ester group-containing acid dianhydride at a reaction temperature that can be industrially used from a raw material that is inexpensive and has few environmental hygiene problems. For the purpose of providing a production method for obtaining a product derivative, a lower alkanoic acid ester of an aromatic diol represented by the general formula (1) and a trimetic acid anhydride represented by the formula (3) are used in the presence of an amine compound. Provided is a method for producing an ester group-containing acid dianhydride derivative represented by the general formula (4), which comprises reacting in an organic solvent.

Description

The present invention relates to a method for producing an ester group-containing acid dianhydride derivative represented by the general formula (4) described later, which is useful as a raw material for a polyesterimide resin or the like.

The ester group-containing acid dianhydride derivative is useful as a raw material for a heat-resistant resin such as polyesterimide, a curing agent such as an epoxy resin, or a resin modifier, and is used as a material for the electric and electronic fields. Examples of the method for producing these include (i) a method by reacting trimellitic anhydride chloride with diols in an organic solvent such as benzene and toluene (see, for example, Patent Document 1), or trimellitic anhydride. In the transesterification reaction between diols and lower alkanoic acid esters of diols, (ii) a method performed by heating in a high temperature region of 280 ° C. in the presence of a specific solvent (see, for example, Patent Document 2), or (iii). A method performed in the presence of an inorganic compound-based catalyst such as a silica-alumina compound or an alkali metal compound (see, for example, Patent Document 3) and a method performed in the presence of an interphase transfer catalyst such as (iv) a phosphonium salt (for example, patent). Reference 4) and the like are known.

Special Publication No. 43-5911 Japanese Unexamined Patent Publication No. 10-147582 Japanese Unexamined Patent Publication No. 7-41472 Japanese Unexamined Patent Publication No. 2006-206486

Toshiba Review Vol.51 No.8 p.58-61 2000

The method disclosed in the background technique (i) must use trimellitic anhydride chloride, which is expensive and difficult to handle in terms of environmental hygiene. The method disclosed in (ii) has a problem that it requires a high temperature at which the reaction is industrially difficult. In the method disclosed in (iii), it is difficult to remove the inorganic compound-based catalyst used, and it tends to become an impurity of the obtained ester group-containing acid dianhydride derivative. Further, in the method disclosed in (iv), the reaction rate at 4 hours after the reaction is not satisfactory as 80 to 86%, and since a phosphonium salt is used, the obtained ester group-containing acid is contained in an anhydride derivative. Phosphorus may remain in the. In particular, if alkali metal or aluminum derived from an inorganic compound catalyst or phosphorus derived from a phase transfer catalyst remains in a material for semiconductors, oxide film pressure resistance failure, p-reversal failure, and n-reversal failure occur in the semiconductor element. It adversely affects the yield and reliability of products (see, for example, Non-Patent Document 1). The present invention provides a production method for efficiently reacting in a short time at an industrially available reaction temperature.

（式中、Ａｒは、下記式（２）：

で表される群から選ばれる２価の芳香族基を表し、
Ｒ_１、Ｒ_２は、同一または異なって、炭素数１〜３のアルキル基を表し、
そしてＲ_３は、同一または異なって、水素原子または炭素数１〜３のアルキル基を表す）
で示される芳香族ジオールの低級アルカン酸エステルと、式（３）：

で示されるトリメット酸無水物を、アミン化合物の存在下、有機溶媒中で反応させることを特徴とする
下記一般式（４）：

（式中、Ａｒは、上記と同義である）
で示される化合物の製造方法に関する。As a result of diligent studies in view of the above problems, the present inventors have obtained an ester group-containing acid dianhydride derivative represented by the general formula (4), which is useful as a raw material for polyesterimide resins and the like, as a lower alkane of an aromatic diol. We have found that an acid ester and a trimellitic anhydride can be efficiently produced by carrying out an ester exchange reaction in a solvent in the presence of an amine compound, and have completed the present invention.
That is, the present invention is as follows.
[1] The following general formula (1):

(In the formula, Ar is the following formula (2):

Represents a divalent aromatic group selected from the group represented by
R ₁ and R ₂ represent alkyl groups having 1 to 3 carbon atoms, which are the same or different.
And R ₃ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
The lower alkanoic acid ester of the aromatic diol represented by the formula (3):

The following general formula (4), which comprises reacting the trimetic anhydride represented by (1) in an organic solvent in the presence of an amine compound:

(In the formula, Ar is synonymous with the above)
The present invention relates to a method for producing a compound represented by.

The ester group-containing acid dianhydride derivative of the present invention is used as a raw material for a heat-resistant resin such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier. The present invention is extremely useful because it can be efficiently produced in a short time from a raw material that is inexpensive and has few environmental hygiene problems in the presence of an amine compound at an industrially usable reaction temperature. The compound obtained by using the present invention is particularly useful as a material for the electric and electronic fields because it is unlikely that impurities such as catalyst-derived metals and phosphorus elements that adversely affect the semiconductor element remain.

Hereinafter, embodiments of the present invention will be described in detail. First, terms used in the present specification and claims will be described. Unless otherwise noted, each term has the following meanings:

In the present invention, the "alkyl group having 1 to 3 carbon atoms" means a linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms, and specifically, a methyl group, an ethyl group, or a propyl group. , Isopropyl group.
In the present invention, the "alkyl group having 1 to 10 carbon atoms" means a linear, branched or cyclic saturated hydrocarbon group having 1 to 10 carbon atoms, and the above-mentioned "alkyl group having 1 to 3 carbon atoms". , Butyl group, pentyl group, hexyl group, octyl group, decyl group, isomers thereof and the like can be exemplified.

In the present invention, the "aryl group" means a monocyclic or polycyclic aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

In the present invention, the "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present invention, the "hydroxyalkyl group having 1 to 10 carbon atoms" means the "alkyl group having 1 to 10 carbon atoms" substituted with at least one hydroxy group, and the hydroxymethyl group, 1-hydroxyethyl group, and the like. 2-Hydroxyethyl group and the like can be exemplified.

Next, the production method of the present invention will be described in detail.

（式中、Ａｒは下記式（２）：

で表される群から選ばれる２価の芳香族基を表し、
Ｒ_１、Ｒ_２は同一または異なって、炭素数１〜３のアルキル基を表し、
そしてＲ_３は、同一または異なって、水素原子または炭素数１〜３のアルキル基を表す）
で示される芳香族ジオールの低級アルカン酸エステルと、式（３）：

で示されるトリメット酸無水物を、アミン化合物の存在下、有機溶媒中で反応させることを特徴とする
下記一般式（４）：

（式中、Ａｒは、上記と同義である）
で示される化合物の製造方法に関するものである。The present invention has the general formula (1):

(In the formula, Ar is the following formula (2):

Represents a divalent aromatic group selected from the group represented by
R ₁ and R ₂ are the same or different and represent alkyl groups having 1 to 3 carbon atoms.
And R ₃ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
The lower alkanoic acid ester of the aromatic diol represented by the formula (3):

The following general formula (4), which comprises reacting the trimetic anhydride represented by (1) in an organic solvent in the presence of an amine compound:

(In the formula, Ar is synonymous with the above)
It relates to the manufacturing method of the compound shown by.

In the general formula (1), R ₁ and R ₂ are the same or different, and are alkyl groups having 1 to 3 carbon atoms, preferably all methyl groups.

で表し、Ｒ_３は、同一または異なって、水素原子または炭素数１〜３のアルキル基であり、水素原子またはメチル基であるものが好ましく、全て水素原子であるものがより好ましい。In the general formula (1)

Expressed in, R ₃ are the same or different, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably has a hydrogen atom or a methyl group, it is more preferable that all hydrogen atoms.

The compound represented by the above general formula (1) used in the production method of the present invention can be commercially available or synthesized by a method known to those skilled in the art. For example, the compound represented by the above general formula (1) can be easily synthesized by heating and reacting a lower alkanoic anhydride with an aromatic diol. At this time, a conventionally known esterification catalyst such as sodium p-toluenesulfonate can also be used.
Here, examples of the lower alkanoic anhydride include acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride, and acetic anhydride is preferable. Aromatic diols include hydroquinone, resorcinol, pyrocatechol, 4,4'-biphenyldiol, 2,2'-biphenyldiol, 3,4'-biphenyldiol, 4,4'-dihydroxydiphenyl ether, 2,2'-. Examples of dihydroxydiphenyl ethers, or those in which these aromatic rings are the same or differently substituted with a methyl group, an ethyl group, a propyl group or an isopropyl group, are exemplified, but hydroquinone, resorcinol, methylhydroquinone, 2, 2 '-Biphenyldiol and the like can be mentioned.

The amount of trimellitic acid anhydride used in the production of the present invention is not particularly limited, but it is preferably used in the range of 1 to 5 mol with respect to 1 mol of the compound represented by the general formula (1), and impurity control. From the viewpoint of workability and workability, it is preferable to use 1.8 to 2.4 mol.

（式中、Ｒ_４、Ｒ_５、Ｒ_６は、同一または異なって、炭素数１〜１０のアルキル基、置換されてもよいピリジル基またはアリール基を表す）
で示される化合物である。Ｒ_４、Ｒ_５、Ｒ_６は、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、デシル基、置換されてもよいピリジル基、フェニル基等が挙げられる。ここで「置換されてもよいピリジル基」は、例えば、非置換の２−、３−または４−ピリジル基、あるいは炭素数１〜１０のアルキル基、アリール基、ハロゲン原子、アミノ基、ニトリル基、炭素数１〜１０のヒドロキシアルキル基およびカルボキシ基からなる群より選択される少なくとも１つの基で置換された２−、３−または４−ピリジル基等が挙げられる。一般式（５）で示される化合物は、具体的には、４−ジメチルアミノピリジン、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、ジメチル（オクチル）アミン、トリオクチルアミン等が挙げられ、これらの化合物を単独でまたは２種類以上混合してもよい。The amine compound used in the production of the present invention is not particularly limited and may be a primary, secondary or tertiary amine compound, but a tertiary amine compound is preferable from the viewpoint of reactivity. More preferably, the following general formula (5):

(In the formula, R ₄ , R ₅ , and R ₆ represent the same or different alkyl groups having 1 to 10 carbon atoms, and optionally substituted pyridyl groups or aryl groups).
It is a compound indicated by. R ₄ , R ₅ , and R ₆ are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, Examples thereof include a decyl group, a pyridyl group which may be substituted, a phenyl group and the like. Here, the "optionally substituted pyridyl group" is, for example, an unsubstituted 2-, 3- or 4-pyridyl group, or an alkyl group having 1 to 10 carbon atoms, an aryl group, a halogen atom, an amino group, or a nitrile group. , 2-, 3- or 4-pyridyl groups substituted with at least one group selected from the group consisting of hydroxyalkyl groups having 1 to 10 carbon atoms and carboxy groups. Specifically, the compound represented by the general formula (5) is 4-dimethylaminopyridine, triethylamine, tripropylamine, triisopropylamine, tributylamine, tripentylamine, trihexylamine, dimethyl (octyl) amine, tri. Examples thereof include octylamine, and these compounds may be used alone or in combination of two or more.

The amount of the amine compound used in the production of the present invention is not particularly limited, but it is preferably used in the range of 0.1 to 10 mol% with respect to 1 mol of the compound represented by the general formula (1), and is 0. . More preferably, it is used in the range of 5 to 1.0 mol%.

An organic solvent is used for the reaction of the present invention. The solvent used has a boiling point near the reaction temperature (170 to 250 ° C.) or exceeds the reaction temperature, and is appropriately selected according to the set reaction temperature, but is not particularly limited as long as it is an inert solvent for the reaction. The solvent may be used alone or in admixture of two or more in any proportion. Specifically, polychlorinated benzene such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, and polychlorinated toluene such as 2,3-dichlorotoluene can be used. Dehydrated aprotic polar solvents such as sulfolane, N-methylpyrrolidone can also be used. The amount of the solvent used is 2 to 10 times (weight basis), preferably 3.75 to 7.2 times (weight basis) the lower alkanoic acid ester of the aromatic diol represented by the general formula (1). is there.

The reaction temperature of the present invention is not particularly limited, but is preferably 170 to 250 ° C., more preferably 200 to 220 ° C. from the viewpoint of reactivity.

The reaction time of the present invention can be appropriately set according to conditions such as the amount and type of starting material used, the type of solvent, and the reaction temperature. Usually, it is preferably 2 to 48 hours, and preferably 12 to 24 hours from the viewpoint of workability.

After completion of the reaction, the obtained reaction solution can be post-treated by a usual method. The method of post-treatment is not particularly limited, but the reaction mixture is subjected to an appropriate post-treatment operation known to those skilled in the art such as filtration and washing to obtain a compound represented by the general formula (4). If desired, the compound represented by the general formula (4) may be purified by subjecting it to further purification means known to those skilled in the art such as recrystallization and column chromatography according to the properties of the desired product.

Examples are shown below to clarify aspects of the present invention, but the present invention is not limited to the examples shown here.

The reaction solutions and crystals obtained in Examples and Comparative Examples were subjected to high performance liquid chromatography analysis, and the reaction purity or the purity of the target product was calculated as an area percentage. Here, the reaction purity means the ratio of the target product (compound represented by the formula (4)) in the reaction solution (excluding the solvent). The measurement conditions are as follows.

<HPLC conditions>
Sample preparation: The sample was added to the eluent, boiled to dissolve it, and then cooled to prepare a measurement sample.
Detector: SPD-20A (manufactured by Shimadzu Corporation)
Oven: CTO-20A (manufactured by Shimadzu Corporation)
Pump: LC-20AD (manufactured by Shimadzu Corporation)
Column: TSKgel ODS-80TM (manufactured by Tosoh Corporation)
4.6 mm ID x 25 cm, 0.5 μm
Eluent: Acetonitrile: Water: Phosphoric acid = 450: 550: 0.5
Column temperature: 40 ° C
Flow velocity: 1.0 mL / min
Detection wavelength: 254 nm

The crystals obtained in Examples and Comparative Examples were subjected to ICP emission spectroscopic analysis to measure the phosphorus content in the crystals. The measurement conditions are as follows.

<ICP emission spectroscopic analysis conditions>
Sample preparation: 0.05 g of the sample was dissolved in 25 mL of NMP to prepare a measurement sample.
Model: SPS3500DD (manufactured by SII Nanotechnology Inc.)

<Example 1>
1,4-Diacetoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.00 g (5.15 mmol), trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.08 g (10.83 mmol), 4 -Add 6.3 mg (0.052 mmol) of dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.8 g of 1,2,4-trichlorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) for 2 hours at 210-220 ° C. It was reacted. The reaction purity at this point is shown in Table 1.

<Examples 2 to 3, Comparative Example 1>
The reaction was carried out in the same manner as in Example 1 except that 4-dimethylaminopyridine was changed to the compound shown in Table 1, and the reaction purity was measured. The results are shown in Table 1.

<Example 4>
In the reactor, 1,4-diacetoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 36.1 g (0.186 mol), trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 75.0 g (0.390 mol), 4 -Dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 114 mg (0.930 mmol) and 135 g of 1,2,4-trichlorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and reacted at 210-220 ° C. for 24 hours. The reaction solution was cooled to obtain a slurry solution of the target product. The slurry solution was filtered and the obtained crystals were dried to obtain 82.5 g of p-phenylenebis (trimellitic acid anhydride) (purity 98.33%, yield 96.8%).
When the phosphorus content of the crystals obtained by ICP emission spectroscopic analysis was confirmed, phosphorus was not confirmed.

<Comparative example 2>
The same procedure as in Example 4 was carried out except that 4-dimethylaminopyridine was changed to tetraphenylphosphonium bromide to obtain 78.9 g of p-phenylenebis (trimellitic anhydride) (purity 98.24). %, Yield 92.6%). When the phosphorus content of the crystal obtained by ICP emission spectroscopic analysis was confirmed, the content was 34 ppm.

<Example 5>
In the reactor, 4,4'-diacetoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.1 g (0.0929 mol), trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 37.5 g (0.1952 mol), Add 56.8 mg (0.465 mmol) of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 94.5 g of 1,2,4-trichlorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and add 2 at 210-220 ° C. Reacted for time. Table 2 shows the reaction purity at this point.

<Comparative example 3>
The reaction was carried out in the same manner as in Example 5 except that 4-dimethylaminopyridine was changed to the compound shown in Table 2, and the reaction purity was measured. The results are shown in Table 2.

<Example 6>
2,5-Diacetoxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.07 g (5.14 mmol), trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.08 g (10.83 mmol), 4 -Add 6.3 mg (0.052 mmol) of dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.8 g of 1,2,4-trichlorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) for 2 hours at 210-220 ° C. It was reacted. The reaction purity at this point was 53.20%.

The ester group-containing acid dianhydride derivative obtained by the production method of the present invention can be used as a polyesterimide resin raw material, a curing agent such as an epoxy resin, or a resin modifier, and is particularly useful as a polyesterimide raw material having a low water absorption rate. .. Polysellimide, which improves the water absorption rate, which is a drawback of polyimide, is extremely useful as an insulating material for the electronic field such as a high-frequency compatible multilayer flexible printed circuit board. The present invention provides a production method for efficiently reacting an ester group-containing acid dianhydride derivative, which is a raw material thereof, from an inexpensive raw material having few environmental health problems at an industrially usable reaction temperature in a short time. It is to provide. Further, the ester group-containing acid dianhydride derivative obtained by the production method of the present invention is particularly suitable for the electric and electronic fields because it is unlikely that impurities such as catalyst-derived metals and phosphorus elements that adversely affect semiconductor devices remain. It is useful as a material for.

Claims (2)

The following general formula (1):

(In the formula, Ar is the following formula (2):

Represents a divalent aromatic group selected from the group represented by
R ₁ and R ₂ represent alkyl groups having 1 to 3 carbon atoms, which are the same or different.
And R ₃ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
The lower alkanoic acid ester of the aromatic diol represented by the formula (3):

The following general formula (4), which comprises reacting the trimetic anhydride represented by (1) in an organic solvent in the presence of a tertiary amine compound:

(In the formula, Ar is synonymous with the above)
It is a method for producing a compound shown by
The tertiary amine compound has the following general formula (5):

(In the formula, R ₄ , R ₅ , and R ₆ represent the same or different alkyl groups having 1 to 10 carbon atoms, and optionally substituted pyridyl groups or aryl groups).
However, a production method excluding a tertiary amine compound containing a total of 10 to 40 carbon atoms. The production method according to claim 1, wherein the amount of the amine compound added is 0.1 to 10 mol% with respect to 1 mol of the compound represented by the general formula (1).