JPH05320172A - Disiloxanetetracarboxylic dianhydride and its production - Google Patents

Abstract

PURPOSE:To provide a disiloxanetetracarboxylic dianhydride useful as a curing agent for epoxy resins, a raw material for polyimide resins, etc. CONSTITUTION:The compound of formula I or formula II (X is chlorine or bromine). For example, 1,3-bis(2,3-dicarboxybicyclo[2,2,1]hept-5-ylmethyl)-1,1,3,3- tetramethyldisiloxane dianhydride. The compound of formula I is obtained e.g. by reacting 5-methylenenorbornane-2,3-dicarboxylic anhydride with 1,1,3,3- tetramethyldiciloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel compounds useful for applications such as epoxy resin curing agents and raw materials for polyimide resins, their intermediates, and methods for producing them.

[0002]

2. Description of the Related Art Silicon-based anhydrides are used as raw materials for various polymers such as epoxy resin curing agents and polyimide resin.
Furthermore, it is useful as an adhesion promoter for polysiloxane compositions, and various silicon-based anhydrides have been developed so far. For example, in JP-A-59-501208, a silyl norbornane carboxylic acid anhydride in which silicon is directly bonded to a norbornane or oxabicycloheptane ring, for example, 1,3-bis (2,3-dicarboxybicyclo [2.
2.1] Hept-5-yl) -1,1,3,3-tetramethyldisiloxane dianhydride and norbornenecarboxylic acid anhydride and 1,1,3,3-tetramethyldisiloxane as a platinum catalyst Disclosed is a method for producing the above compound by reacting in the presence of In addition, JP-A-61-1
No. 56189, 1,3-bis (2,3-dicarboxybicyclo [2.2], wherein 5-norbornene-2,3-dicarboxylic acid anhydride is reacted with dimethylchlorosilane to hydrolyze the product. .1] pept-5-yl)
A method of making -1,1,3,3-tetramethyldisiloxane dianhydride is disclosed.

[0003]

Although the silicon-based anhydride can be used for various purposes as described above, it has a drawback that its production is difficult. For example, few methods have been reported for synthesizing a silicon-based anhydride by directly reacting an acid anhydride with silane or siloxane. Special Table Sho 59-5
The anhydride or dianhydride described in Japanese Patent No. 01208 can be prepared by directly reacting an acid anhydride with a silane or a siloxane, but it generally requires a reaction at a high temperature for a long time. Japanese Patent Application Laid-Open No. 61-56189 discloses a method in which the reaction time is shortened, but does not disclose a method for producing siloxane dianhydride by a direct reaction between an acid anhydride and siloxane.

[0004]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a novel siloxane dianhydride which is easy to prepare, an intermediate silane dianhydride, and a method for producing them.

The present invention firstly provides the following formula (I):

[Chemical 3] A compound represented by the formula: 1,3-bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl) -1,1,3,3-tetramethyldisiloxane dianhydride (hereinafter , Compound I may be abbreviated).

1,3-bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl) -1,
1,3,3-tetramethyldisiloxane dianhydride includes:
Regarding the bond between the norbornane ring and the acid anhydride, endo
There are three structures, -endo, exo-exo, and endo-exo, each of which has two additional diastereomers, but all of them and mixtures thereof are included in the present invention.

This compound is useful as a raw material for various polymers such as epoxy resin curing agents and polyimide resins, and as an adhesion promoter for polysiloxane compositions.

The present invention secondly provides a process for preparing the above compound I. Compound I is 5-methylene norbornane-
It can be prepared by reacting 2,3-dicarboxylic anhydride with 1,1,3,3-tetramethyldisiloxane.

5-Methylenenorbornane-2,3-dicarboxylic acid anhydride is 5-methylnorbornene-2,3-
It can be easily prepared by isomerization of dicarboxylic acid anhydride and / or 1-methylnorbornene-2,3-dicarboxylic acid anhydride in the presence of an acid catalyst. here,
“Isomerization” broadly includes structural isomerization and stereoisomerization, and does not have a narrow meaning such as geometrical isomerization or positional isomerization. 5-methylenenorbornane-2,3-dicarboxylic acid anhydride has two endo and exo forms.
Either of these may be used in the present invention. It is also possible to use a mixture of both.

1-Methylnorbornene-2,3-dicarboxylic acid anhydride and 5-methylnorbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as 1-MeNA and 5-Me, respectively).
Sometimes abbreviated as NA. ) Itself is known. Both of these two acid anhydrides have two stereoisomers, an endo isomer and an exo isomer, and either of them can be used.

5-MeNA and 1-MeNA as raw materials
Can be manufactured, for example, as follows. That is, 1-methylcyclopentadiene (1-MeCPD
Abbreviated. ) And 2-methylcyclopentadiene (2-M
Abbreviated as eCPD. Is reacted with maleic anhydride (Diels-Alder reaction), 1-MeCPD produces an endo form of 1-MeNA and 2-MeCPD forms an endo form of 5-MeNA. 1-MeCPD
And 2-MeCPD are usually obtained as a mixture of the two, and it is not necessary to separate the two for the purposes here.

1-MeNA and 5-M thus obtained
When the mixture of eNA is subjected to isomerization described below, 1-
The endo form of MeNA produces the exo form of 5-methylenenorbornane-2,3-dicarboxylic acid anhydride via the exo form of 5-MeNA, while the endo form of 5-MeNA directly forms the exo form of 5-MeNA. -Methylene norbornane-2,
An endo form of 3-dicarboxylic anhydride is produced. Also, some endo-forms of 5-MeNA are
5-methylenenorbornane-2, via the exo form of
An exo form of 3-dicarboxylic acid anhydride is produced. 1
When the following heating is performed in the absence of an acid on the endo form of MeNA, isomerization occurs to the exo form of 5-MeNA, but it is further converted to the exo form of 5-methylenenorbornane-2,3-dicarboxylic acid anhydride. It does not isomerize.

Methyl norbornene-2,3-dicarboxylic acid anhydride is generally commercially available, and it is also possible to use this.

The isomerization reaction is carried out by using 5-methylnorbornene-
It can be carried out by heating 2,3-dicarboxylic acid anhydride and / or 1-methylnorbornene-2,3-dicarboxylic acid anhydride in the presence of an acid.

The acid used for the isomerization reaction is not particularly limited, and various known acids can be used. Examples include Bronsted acids, for example, aromatic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid, and paraxylene-2-sulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, heteropolyacids such as molybdic acid, and carboxylic acids such as maleic acid. Examples of the acid include Lewis acids other than the above, such as aluminum chloride and boron fluoride. Moreover, since an acid anhydride such as maleic anhydride can react with water to generate an acid, the isomerization reaction may proceed even if an acid anhydride is used instead of the acid. In the present invention, it is preferable to use Bronsted acid. The amount of acid used is methyl norbornene-
It is preferably about 0.01 to 5% by weight, particularly about 0.02 to 3% by weight, based on 2,3-dicarboxylic acid anhydride.

The temperature during heating is preferably about 120-.
250 ° C, especially about 150-230 ° C. The isomerization reaction by heating can be carried out batchwise or continuously. The reaction time is preferably about 30 in the case of a batch system.
Minutes to 10 hours, especially about 1 to 5 hours.

1,1,3,3-Tetramethyldisiloxane is known, and commercially available products can be used.

When 5-methylenenorbornane-2,3-dicarboxylic anhydride and 1,1,3,3-tetramethyldisiloxane are reacted, the ratio of the two is arbitrary, but a molar ratio of 2: 1. Is preferred. This reaction is carried out in the presence of a catalyst. Examples of preferable catalysts include, but are not limited to, benzoyl peroxide, organic peroxides such as 2,2′-azobis (isobutylnitrile), and metals such as platinum and palladium and complexes thereof. Particularly preferred are platinum complexes, especially chloroplatinic acid and its salts. The catalyst concentration is 10 with respect to 1 mol of 5-methylenenorbornane-2,3-dicarboxylic anhydride.
^-3 to 10 ^-6 mol, more preferably 10 ^-4 to 10 mol
^-5 mol. This reaction can also be carried out in any solvent. Preferred solvents include, but are not limited to, benzene, toluene, chlorobenzene, xylene, tetrahydrofuran and the like. This reaction is 5
2 to 20 at a temperature of 0 to 200 ° C., especially 70 to 150 ° C.
It is preferable to carry out the treatment for 3 to 15 hours.

The product obtained as described above may be subjected to a purification treatment. Purification can be performed by removing the volatiles under reduced pressure.

Compound I can also be prepared by reacting 5-methylenenorbornane-2,3-dicarboxylic anhydride with dimethylhalosilane and then with water.

In the present invention, a dimethylhalosilane having preferably chlorine or bromine is used. These silanes are known, and commercially available products can be used. The reaction between the silane and 5-methylenenorbornane-2,3-dicarboxylic acid anhydride is preferably carried out in the presence of a catalyst at 50 to 200 ° C. for 2 to 20 hours. The preferred catalyst and its concentration may be the same as described above for the reaction of 5-methylenenorbornane-2,3-dicarboxylic anhydride with disiloxane. This reaction also proceeds in the absence of a solvent, but it can also be carried out using any solvent such as benzene, toluene, chlorobenzene, xylene and tetrahydrofuran.

The hydrolytic dimerization reaction between the product obtained above and water is carried out at 50 to 150 ° C. for 10 minutes to 3 hours in the presence of a stoichiometric amount or more of water relative to the product. Is preferred. This reaction proceeds without a solvent, but any benzene, toluene, tetrahydrofuran, ether,
It can also be carried out in a solvent such as methylene chloride, chloroform, methanol or ethanol. The product thus obtained can also be purified by removing the volatiles under reduced pressure.

The invention also relates to dimethylhalosilanes, especially dimethylchlorosilane or dimethylbromosilane, and
The following formula (II) obtained by the above reaction with methylene norbornane-2,3-dicarboxylic acid anhydride:

[Chemical 4] (In the formula, X represents chlorine or bromine), that is, (2,3-dicarboxybicyclo [2.
2.1] Hept-5-ylmethyl) dimethylhalosilane anhydride is provided.

(2,3-dicarboxybicyclo [2.
2.1] hept-5-toylmethyl) dimethylhalosilane anhydride (hereinafter, may be abbreviated as compound II) has two forms, an endo form and an exo form. Including mixtures.

Compound II can be prepared by the above reaction, but the product obtained by the reaction may be further purified.

The compound of the present invention can be identified by infrared absorption spectrum (IR), ¹ H-NMR and the like. For example, 1,3-bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl) -1,1,
In the IR of 3,3-tetramethyldisiloxane dianhydride, 1770 to 1780 cm ⁻¹ and 1850 cm
^The peak due to C = 0 stretching of the acid anhydride at ^-1 is 10
Peak due to stretching of Si—O—Si at 00 to 1100 cm ⁻¹ (this peak represents 5-methylenenorbornane-2,3-dicarboxylic acid anhydride as a starting material and an intermediate (2,3-dicarboxybicyclo). [2.2.1] Hept-5-ylmethyl) dimethylhalosilane anhydride is not observed.) Is observed. Also, its ¹ H-NMR
In δ0.06, a peak of 12H due to the proton of the methyl group bonded to silicon (δ is not observed in the starting material, 5-methylenenorbornane-2,3-dicarboxylic acid anhydride) is observed at δ0. 63 -C _{H 2} silicon-bonded - peak 4H content of (5-methylene-2,3-dicarboxylic anhydride of this peak starting material, 1,1,3,3-tetramethyl disiloxane and dimethyl (Not observed with halosilane), but δ
In 1.2 to 1.4, a peak 8H component due to four —C H ₂ — of the norbornane ring and a peak 10H component due to 10> C H − in δ1.6 to 3.1 are ( No two peaks are observed for the starting materials 1,1,3,3-tetramethyldisiloxane and dimethylhalosilane, and their ratio is 4H for 5-methylenenorbornane-2,3-dicarboxylic anhydride. : 4H) Observed. On the other hand, a peak due to H ₂ C = C <(2H is observed in the starting material 5-methylenenorbornane-2,3-carboxylic acid anhydride) and a peak due to a proton directly bonded to silicon (starting Substance 1,1,3,3
-For tetramethyldisiloxane and dimethylhalosilane, 2H and 1H minutes are observed respectively. ) Is not observed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0028]

【Example】

[Reference Example] 5 equipped with a reflux condenser, a thermometer, and a stirrer
In a 00 ml four-necked flask, 300 g of endo-methylnorbornene-2,3-dicarboxylic anhydride (5
It consists of 8.5% of 1-methyl form and 41.5% of 5-methyl form. ) And 0.15 g of paratoluene sulfonic acid were introduced, and the mixture was reacted by stirring at 180 ° C. for 3 hours. Simple distillation yielded 287 g of a pale yellow, transparent liquid, which was separated from the catalyst and heavy by-products. When the composition of this liquid was analyzed by gas chromatography, it was found to be 8.
8% endo-5-methylenenorbornane-2,3-
It was found to consist of dicarboxylic anhydride, 63.5% exo-5-methylenenorbornane-2,3-dicarboxylic anhydride, and 27.7% unreacted methylnorbornene-2,3-dicarboxylic anhydride. did. The structure of the product was identified by infrared absorption spectrum (IR), ¹ H-NMR and the like. For example, in the IR of the compound,
At 1770 to 1780 cm ⁻¹ and 1850 cm ⁻¹ , peaks due to C═O stretching of carboxylic acid anhydride were observed. In ¹ H-NMR, a peak due to H ₂ C = C <at δ 4.8 to 5.2 (this peak is not observed in the starting material methylnorbornene-2,3-dicarboxylic acid anhydride). However, a peak of 4H due to —CH ₂ — in δ1.8 (2H in the starting material) was δ2.8.
A peak due to a proton bonded to the tertiary carbon atom of the norbornane ring was observed at ˜3.6. No peak due to = CH- of the norbornene ring was observed.

[0029]

Example 1 0.20 mol of 5-methylenenorbornane-2,3-dicarboxylic acid anhydride and 0.10 mol of 1,1,3,3-tetramethyldisiloxane were dissolved in 10 ml of toluene and chlorinated. 0.26 ml of a solution of platinum acid in isopropanol (concentration: 7.7 × 10 ⁻⁵ mol / ml) was added, and the mixture was heated at 90 ° C. for 10 hours. After cooling to room temperature, the volatile matter was completely removed by a vacuum pump to obtain a colorless oil quantitatively.

The elemental analysis values of the oily substance are shown below. still,
Numerical values in parentheses are 1,3-bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl)-
It is a calculated value when 1,1,3,3-tetramethyldisiloxane dianhydride is used. C: 58.41% (58.7%) H: 7.09% (6.98%)

Further, with respect to the above oily substance, ¹ H-NM
R and IR were measured. ¹ H-NMR shows oily product as CDC
and l ₃ solution was measured CHCl ₃ as a reference. IR
Was measured by sandwiching the oily substance between KBr discs. The measurement results are shown in FIGS. 1 and 2, respectively.

In ¹ H-NMR of FIG. 1, δ0.06
A peak attributed to the proton of methyl group bonded to silicon is observed 12H min, -C _{H 2} silicon-bonded δ0.63 to - a peak attributed to the observed 4H minute, δ1.2~1. The peak 8H content attributable to four —C H ₂ — in 4 and the peak 10H content attributable to 10> C H − in δ1.6 to 3.1 were observed. , 3-bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethylto) -1,1,
It was identified as 3,3-tetramethyldisiloxane dianhydride. The peak at δ7.25 in FIG. 1 is due to C H Cl ₃ in CDCl ₃ used as a solvent in the measurement. The above conclusion is that in the IR of FIG. 2, 1770 to 1780 cm ⁻¹ and 1850 cm ^−1.
The peak due to the C = O stretching of the acid anhydride is 1000
It is also supported by the fact that a peak due to stretching of Si—O—Si is observed at ˜1100 cm ⁻¹ and by the result of elemental analysis.

[0033]

Example 2 0.20 mol of 5-methylenenorbornane-2,3-dicarboxylic acid anhydride and 0.20 mol of dimethylchlorosilane were dissolved in 10 ml of toluene, and a solution of chloroplatinic acid in isopropanol (concentration: 7.7). × 10 ^-5
(Mol / ml) 0.26 ml was added and heated in a sealed tube at 90 ° C. for 10 hours. After cooling to room temperature, it was distilled under reduced pressure, and the fraction was allowed to stand at room temperature to give colorless crystals.

From its IR, ¹ H-NMR and elemental analysis values, the obtained colorless crystals were (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl) dimethylchlorosilane anhydride. There was found.

Next, 0.10 mol of this colorless crystal was added to 110 ° C.
Was heated and melted, 0.15 mol of water was added, and the mixture was heated and stirred for 2 hours. After heating, the volatiles were completely removed under reduced pressure to give a colorless oil.

From IR, ¹ H-NMR and elemental analysis values,
The oily matter was 1,3 bis (2,3-dicarboxybicyclo [2.2.1] hept-5-ylmethyl) -1,
It was found to be 1,3,3-tetramethyldisiloxane dianhydride.

[0037]

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound, 1,3-
Bis (2,3dicarboxybicyclo [2.2.1] hept-5-ylmethyl) -1,1,3,3-tetramethyldisiloxane dianhydride (Compound I), and (2,3-dicarboxy Bicyclo [2.2.1] hept-5-ylmethyl) dimethylhalosilane anhydride (Compound II) was provided. Compound I is 5-methylene norbornane-2,
By reacting 3-dicarboxylic anhydride with 1,1,3,3-tetramethyldisiloxane, or 5
It can be prepared by reacting methylenenorbornane-2,3-dicarboxylic anhydride with dimethylhalosilane and then with water. Compound II
Can be prepared by reacting 5-methylenenorbornane-2,3-dicarboxylic acid anhydride with dimethylchlorosilane and / or dimethylbromosilane. Compound I is easy to prepare and is useful for various applications such as a raw material for epoxy resin curing agents and polyimide resins.

[Brief description of drawings]

FIG. 1 is ¹ H—N of the oily substance obtained in Example 1.
It is a chart of MR. The number immediately below the peak indicates the integrated value of the peak in the range designated by the polygonal line, and the number below it indicates the chemical shift.

FIG. 2 is an IR chart of the oily substance obtained in Example 1.

Claims (5)

[Claims] 1. The following formula (I): The compound represented by. 2. The following formula (II): (In the formula, X represents chlorine or bromine). 3. A process for producing a compound according to claim 1, which comprises reacting 5-methylenenorbornane-2,3-dicarboxylic acid anhydride with 1,1,3,3-tetramethyldisiloxane. .. 4. A reaction of 5-methylenenorbornane-2,3-dicarboxylic acid anhydride with dimethylhalosilane,
Next, the method for producing the compound according to claim 1, which comprises reacting with water. 5. The method for producing the compound according to claim 2, which comprises reacting 5-methylenenorbornane-2,3-dicarboxylic acid anhydride with dimethylchlorosilane and / or dimethylbromosilane.