JPH11116548A - Bissulfonate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a monomer for production of a polymer containing phenylene group which has excellent heat resistance, low-dielectric property and processability and is soluble in organic solvents. SOLUTION: This compound is represented by formula I [R<1> and R<2> are each a 1-3C alkyl, fluoroalkyl or the like; R<3> to R<6> are each H, F or the like; R<7> is an aryl represented by formula II (R<10> is H, F or the like) or a 1-3C fluoroalkyl; R<8> is H, F or the like; m is 1-5] e.g. bis(4-methylsulfonyloxyphenyl) diphenylmethane. The compound represented by formula I is obtained by a process comprising: dripping a sulfonyl chloride(anhydride) such as methanesulfonyl chloride into a pyridine solution of a bisphenol compound such as bis(4-hydroxyphenyl)diphenylmethane, while keeping the temperature at <=15 deg.C for 5-60 min in a nitrogen flow, agitating for 0-60 min, returning the temperature to room temperature and further agitating for 0-24 h, then reprecipitating the resultant suspension in 3-20 wt. times of ice water followed by recrystallization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound, a bissulfonate compound. More specifically, the present invention relates to a bissulfonate compound which has excellent heat resistance, low dielectric properties, and processability, and is suitable as a monomer for producing a phenylene group-containing polymer which is soluble in an organic solvent.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) have become highly integrated, multifunctional, and high-performance, reflecting the progress of fine processing technology. As a result, the circuit resistance (hereinafter, referred to as “parasitic resistance”) and the capacitance between the wirings (hereinafter, referred to as “parasitic resistance”).
It is called “parasitic capacitance”. ) Increases, the power consumption increases, and the delay time also increases, which is a major factor in reducing the signal speed of the device. Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to cover the periphery of the wiring with an interlayer insulating film to reduce the parasitic capacitance and respond to the speeding up of the device. I have. Therefore, the interlayer insulating film is required to have excellent heat resistance enough to withstand a thin film forming step in manufacturing a mounting substrate, a chip connecting step, a pinning step, and the like.

[0003] Therefore, as this high heat resistant organic material,
Although polyimides are widely known, satisfactory ones have not been obtained in terms of low dielectric properties and low water absorption since they contain imide groups having high polarity. On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. In order to impart solubility to this polyphenylene, a side chain is generally introduced, but the introduction of the side chain causes problems such as a decrease in heat resistance and a complicated production of raw materials. There is.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to efficiently provide a phenylene group-containing polymer that is soluble in an organic solvent having excellent heat resistance, low dielectric properties and processability. It is another object of the present invention to provide a bissulfonate compound as a raw material monomer that can be stably and inexpensively produced.

[0005]

According to the present invention, there is provided a bissulfonate compound represented by the following general formula (I).

[0006]

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[In the formula (I), R ¹ and R ² are an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, or an aryl group represented by the following general formula (II), R ³ , R ⁴ , R
⁵ and R ⁶ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, and R ⁷ is an aryl group represented by the following general formula (III) or R ¹ and R ² , R ³ and R ⁴ and R ^{8 each} represent a hydrogen atom, a fluorine atom, or a C ¹ to C 3 fluoroalkyl group;
⁵ and R ⁶ may be the same or different, and m is an integer of 1 to 5. ]

[0008]

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[In the formula (II), R ⁹ represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 3 carbon atoms. ]

[0010]

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[In the formula (III), R ¹⁰ represents a hydrogen atom, a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms. ]

[0012]

Embodiments of the present invention will be described below in detail. The bissulfonate compound of the present invention is a novel compound represented by the above general formula (I).

Specifically, R ¹ and R ² are methyl, ethyl, propyl, trifluoromethyl, phenyl, p-tolyl, m-tolyl, o-tolyl, p-tolyl, Examples include a fluorophenyl group, an m-fluorophenyl group, an o-fluorophenyl group, and the like. Preferably, a methyl group, a trifluoromethyl group, p
-Fluorophenyl group, p-tolyl group and phenyl group. And particularly preferably, R ¹ and R ² are the same group.

Further, R ³ , R ⁴ , R ⁵ and R ^{6 are} as follows:
A hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a carbon atom having 2 to 5 carbon atoms such as a 1-propenyl group and a 2-propenyl group (allyl group);
And an phenyl group, and a phenyl group. Of these, R ³ , R ⁴ , R ⁵ , and R ⁶ are more preferably a hydrogen atom, a fluorine atom, a methyl group,
-A propenyl group or a phenyl group. These groups are preferably located at the o (ortho) -position with respect to the R ¹ O ₂ SO ^- group or the R ² O ₂ SO ^- group.

R ³ and R ⁵ , and R ⁴ and R ⁶ are preferably the same groups. However, when R ³ is a 2-propenyl group, R ⁴ is preferably a hydrogen atom.

R ⁷ is phenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, perfluorophenyl, p-trifluoromethylphenyl, m-trifluoromethylphenyl, o-trifluoromethylphenyl group, p-pentafluoroethylphenyl group, m-pentafluoroethylphenyl group, o-pentafluoroethylphenyl group, p-
Examples include a heptafluoropropylphenyl group, an m-heptafluoropropylphenyl group, an o-heptafluoropropylphenyl group, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

R ⁸ is specifically a hydrogen atom,
Examples include a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Specific examples of R ⁹ include a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Further, specific examples of R ¹⁰ include a hydrogen atom, a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like. Note that R ⁸ has 1 to 3 carbon atoms.
In the formula, n is 1.

The bissulfonate compound of the present invention has an organic group or a substituent R ^{1 to} R ¹⁰ in the general formula (1),
All combinations selected from the aforementioned organic groups and fluorine atoms. Preferred compounds included in this combination are listed below. That is, bis (4-methylsulfonyloxyphenyl) diphenylmethane, bis (4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis ( 4-trifluoromethylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (4
-Phenylsulfonyloxyphenyl) diphenylmethane, bis (4-phenylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (4
-P-tolylsulfonyloxyphenyl) diphenylmethane, bis (4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane, bis ( 4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane, bis (3-fluoro-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-fluoro -4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-trifluoromethylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (3
-Fluoro-4-phenylsulfonyloxyphenyl)
Diphenylmethane, bis (3-fluoro-4-phenylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane, bis (3-fluoro-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane,
Bis (3-fluoro-4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane,
Bis (3-methyl (4-methylsulfonyloxy) phenyl) diphenylmethane, bis (3-methyl (4-methylsulfonyloxy) phenyl) (trifluoromethyl) (phenyl) methane, bis (3-methyl-4- Trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-methyl-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-methyl-4-phenylsulfonyloxyphenyl) Diphenylmethane, bis (3-
Methyl-4-phenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-methyl-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3-methyl-4-p-tolylsulfate) Phonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-methyl-4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane,
Bis (3-methyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl-4) -Methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4)
-Trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-phenylsulfonyloxyphenyl) ) Diphenylmethane, bis (3-allyl-4-phenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl) -4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-p-
Fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane, bis (3-phenyl-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3-phenyl-4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-phenyl) -4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-phenyl-4-trifluoromethylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (3
-Phenyl (4-phenylsulfonyloxy) phenyl) diphenylmethane, bis (3-phenyl (4-phenylsulfonyloxy) phenyl) (trifluoromethyl) (phenyl) methane, bis (3-phenyl-4-p
-Tolylsulfonyloxyphenyl) diphenylmethane, bis (3-phenyl-4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-phenyl-4-p-fluorophenylsulfonyloxy) Phenyl) diphenylmethane, bis (3-phenyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl)
Methane, bis (3,5-difluoro-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3,5
-Difluoro-4-methylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (3,5-difluoro-4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3,5
-Difluoro-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-difluoro-4-phenylsulfonyloxyphenyl) diphenylmethane, bis (3,5-
Difluoro-4-phenylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (3,5-difluoro-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3,5-difluoro-4-p-tolylsulfonyloxyphenyl) (tri Fluoromethyl) (phenyl) methane, bis (3,5
-Difluoro-4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (3,5-difluoro-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane,
Bis (3,5-dimethyl (4-methylsulfonyloxy) phenyl) diphenylmethane, bis (3,5-dimethyl (4-methylsulfonyloxy) phenyl) (trifluoromethyl) (phenyl) methane, bis (3, 5-
Dimethyl-4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3,5-dimethyl-
4-trifluoromethylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (3,5-dimethyl-4-phenylsulfonyloxyphenyl) diphenylmethane, bis (3,5-dimethyl-
4-phenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-dimethyl-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3,5-dimethyl-4-p- Tolylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane, bis (3,5-dimethyl-4-p
-Fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (3,5-dimethyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-diphenyl-4-methyl) Sulfonyloxyphenyl) diphenylmethane, bis (3,5-diphenyl-4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-diphenyl-4-trifluoromethylsulfonyloxyphenyl) ) Diphenylmethane, bis (3,5-diphenyl-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane, bis (3,5-diphenyl (4-
Phenylsulfonyloxy) phenyl) diphenylmethane, bis (3,5-diphenyl (4-phenylsulfonyloxy) phenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-diphenyl-4-p-tolylsulfate) Phonyloxyphenyl) diphenylmethane, bis (3,5-diphenyl-4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3,5-diphenyl-4-p-fluorophenylsulfoni) Loxyphenyl) diphenylmethane, bis (3,5-diphenyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane and the like.

Particularly preferred examples of the bisfluphonate compound of the present invention are listed below. These are excellent in ease of synthesis and low in dielectric constant of the polymer. Bis (4-methylsulfonyloxyphenyl) diphenylmethane, bis (4-methylsulfonyloxyphenyl)
(Trifluoromethyl) (phenyl) methane, bis (4
-Trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, bis (4-phenyl) Sulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane , Bis (4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (4-p
-Fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-fluoro-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-methylsulfonyloxyphenyl) (tri Fluoromethyl) (phenyl)
Methane, bis (3-fluoro-4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3- Fluoro-4-phenylsulfonyloxyphenyl) diphenylmethane, bis (3-fluoro-4-phenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-fluoro-4-p-tolylsulfonyloxy) Phenyl) diphenylmethane, bis (3-fluoro-4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-fluoro-4-p-fluorophenylsulfonyloxyphenyl) diphenylmethane,
Bis (3-fluoro-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-methylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl- 4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4)
-Trifluoromethylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl-4-trifluoromethylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-phenylsulfonyloxy) Phenyl) diphenylmethane, bis (3-allyl-4-phenylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-p-tolylsulfonyloxyphenyl) diphenylmethane, bis (3 -Allyl-4-p-tolylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane, bis (3-allyl-4-p-
Fluorophenylsulfonyloxyphenyl) diphenylmethane, bis (3-allyl-4-p-fluorophenylsulfonyloxyphenyl) (trifluoromethyl)
(Phenyl) methane and the like.

The bissulfonate compound of the present invention can be prepared, for example, as follows. That is, as a bisphenol compound, for example, bis (4-
Hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane,
Use bis (4-hydroxyphenyl) (trifluoromethyl) (phenyl) methane and the like, and if necessary, dissolve a catalyst such as 4-dimethylaminopyridine and a base in a solvent. Note that pyridine or the like may be used as a solvent so that both roles of the solvent and the base may be used. Then, sulfonic acid chloride (anhydride), for example, methanesulfonic acid chloride, trifluoromethanesulfonic anhydride, p-toluenesulfonic acid chloride, etc.
The solution is added dropwise under a nitrogen stream over 5 to 60 minutes while the temperature is kept at or below ° C. Then, after stirring at that temperature for 0-60 minutes,
Return to room temperature and stir for 0-24 hours to make a suspension.
The obtained suspension is reprecipitated in 3 to 20 times the amount of ice water, the precipitate is recovered, and the operation such as recrystallization is repeated to obtain crystals as crystals.

Alternatively, first, bis (4-hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-
Hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) (trifluoromethyl) (phenyl) methane and the like are dissolved in an aqueous alkali solution such as an aqueous sodium hydroxide solution. On the other hand, sulfonic acid chloride (anhydride), for example, methanesulfonic acid chloride, trifluoromethanesulfonic anhydride and the like are dissolved in an organic solvent such as toluene and chloroform. Then, if necessary, a phase transfer catalyst such as acetyltrimethylammonium chloride is added, and the mixture is reacted. Then, the desired bissulfonate compound can also be obtained by purifying the organic layer obtained by the reaction.

[0022]

EXAMPLES The present invention will be described more specifically with reference to the following examples. The percentages and parts used are by weight unless otherwise specified. Various measurement items in Examples and Reference Examples were obtained as follows.

(H-NMR analysis) Measurement was performed at 90 MHz using N, N-dimethylformamide-d7 as a solvent. (IR analysis) It was measured by the KBr method. (Mass spectrum) direct introduction method (ionization voltage 70e
V).

(Relative Dielectric Constant) A polymer was dissolved in a predetermined solvent, applied to a SUS substrate by spin coating, and then baked under predetermined conditions to form a polymer coating film. Thereafter, a gold electrode was formed by mask evaporation to obtain a sample for measuring a relative dielectric constant. The capacitance of this sample was measured with an LCR meter 4284A (manufactured by Yokogawa Hewlett-Packard), and the relative dielectric constant was determined from the following equation. ε = C · d / (ε ₀ · S) where ε is a relative permittivity, C is a capacitance, d is a film thickness, ε ₀
Represents the dielectric constant in vacuum, and S represents the area of the upper electrode.

[Example 1] (Synthesis of bis (4-methylsulfonyloxyphenyl) diphenylmethane) A three-one motor, a nitrogen inlet tube,
In a four-necked flask equipped with a thermometer and a dropping funnel,
Bis (4-hydroxyphenyl) diphenylmethane 3
5.2 g (100 mmol) and 0.61 g (5 mmol) of 4-dimethylaminopyridine were added to 70 m of pyridine.
After suspending in a mixed solvent of 210 ml of toluene and 34.4 g of methanesulfonic acid chloride (300 mmol)
l) was added dropwise over 30 minutes under a nitrogen stream while maintaining the temperature at 10 ° C or lower. After continuing stirring as it is at 10 ° C. or lower for 30 minutes, it was returned to room temperature and stirred for 24 hours to obtain a reaction solution.
Toluene was added to this reaction solution, and then washed twice with saturated aqueous sodium bicarbonate and once with saturated saline. Then, the toluene layer in the reaction solution was dried using anhydrous magnesium sulfate.

Next, the toluene layer was concentrated, dried and recrystallized from ethyl acetate to obtain white crystals in a yield of 70%. The results of measuring the IR and H-NMR spectra of this crystal are shown in FIGS. 1 and 2, respectively.
When the mass spectrum of this crystal was measured, the parent peak was 508. Therefore, it was confirmed that the white crystals obtained from these measurements were bis (4-methylsulfonyloxyphenyl) diphenylmethane.

Example 2 (Synthesis of bis (3-fluoro-4-methylsulfonyloxyphenyl) diphenylmethane) In a four-necked flask equipped with a three-one motor, a nitrogen inlet tube, a thermometer and a dropping funnel, 38.8 g of (3-fluoro-4-hydroxyphenyl) diphenylmethane (100 mmol
l) was dissolved in 350 ml of pyridine, and 34.4 g (300 mmol) of methanesulfonic acid chloride was added to 10 ml of pyridine.
The solution was added dropwise over 30 minutes under a nitrogen stream while maintaining the temperature at not more than ° C. After stirring was continued at 10 ° C. or lower for 30 minutes, the mixture was returned to room temperature and stirred for 5 hours. The resulting milky suspension was added to 1
The precipitate was reprecipitated in 0 volumes of ice water, and the precipitate was collected and washed with water and methanol. Subsequently, the precipitate was dissolved in chloroform, washed twice with a saturated aqueous sodium bicarbonate solution and once with a saturated saline solution, and then the chloroform layer was dried over anhydrous magnesium sulfate.

Next, the chloroform layer is concentrated and dried.
White crystals were obtained with a yield of 99%. I of this crystal
The results of measuring the R and H-NMR spectra are shown in FIGS. When the mass spectrum of the crystal was measured, the parent peak was 544. Therefore, it was confirmed that the white crystals obtained from these measurements were bis (3-fluoro-4-methylsulfonyloxyphenyl) diphenylmethane.

Example 3 (Synthesis of bis (4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane) Four-necked flask equipped with a three-one motor, a nitrogen inlet tube, a thermometer and a dropping funnel In bis (4-hydroxyphenyl) (trifluoromethyl) (phenyl) methane
After dissolving 4 g (100 mmol) in 350 ml of pyridine, 34.4 g (30 ml) of methanesulfonic acid chloride was dissolved.
0 mmol) was added dropwise over 30 minutes under a nitrogen stream while maintaining the temperature at 10 ° C or lower. After stirring was continued at 10 ° C. or lower for 30 minutes, the mixture was returned to room temperature and stirred for 5 hours. The resulting milky white suspension was reprecipitated in a 10-fold amount of ice water, and the precipitate was recovered and washed with water and methanol. Subsequently, the obtained precipitate was dissolved in chloroform, washed twice with a saturated aqueous sodium bicarbonate solution and once with a saturated saline solution, and dried with anhydrous magnesium sulfate.

Next, the chloroform layer was concentrated, dried and recrystallized from ethyl acetate to obtain white crystals in a yield of 75%. IR, H-NM of this white crystal
The results of measuring the R spectrum are shown in FIGS. 5 and 6, respectively. When the mass spectrum of the obtained white crystal was measured, the parent peak was 500. Therefore, these measurements confirmed that the white crystals were bis (4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane.

[Examples 4 to 7] Instead of methanesulfonic acid chloride, sulfonic acid chlorides (sulfonic anhydrides) shown in Table 1 were used.
6 and 7, the same operation as in Example 3 was performed except that the pyridine solution was used). Table 1 shows the results.

[0032]

[Table 1]

REFERENCE EXAMPLE In a 500 ml three-necked flask equipped with an argon gas inlet tube and a thermometer, 7.5 g of sodium iodide and 1.3 g of anhydrous nickel chloride were placed.
, 15.7 g of triphenylphosphine, 45.8 g of zinc powder activated with acetic acid, and 50% of bis (4-methylsulfonyloxyphenyl) (trifluoromethyl) (phenyl) methane obtained in Example 3. And dried under vacuum overnight. Thereafter, the inside of the three-necked flask was filled with argon gas. Subsequently, 150 ml of dry N, N-dimethylacetamide was added, and the mixture was stirred at 70 ° C. under an argon stream, whereby the reaction solution turned brown. The reaction solution is kept at 70 ° C. for 20 minutes.
After reacting under the conditions of time, this reaction solution was diluted with 36% hydrochloric acid 5
Poured into a mixture of 00 ml and 2000 ml of methanol. Then, a precipitate was generated, and the precipitate was collected. The resulting precipitate was suspended in chloroform and washed with a 2N aqueous hydrochloric acid solution. Thereafter, the chloroform layer was poured into methanol, and the precipitate was recovered and dried to obtain 19 g of a white powdery polymer.

The molecular weight of this white powdery polymer was determined by GPC.
When measured by the method, the weight average molecular weight was 16,600 and the number average molecular weight was 11,400 (in terms of polystyrene). Moreover, the obtained polymer was soluble in cyclohexanone, and a colorless and transparent film was obtained by spin-coating and baking this solution on a glass substrate.

Further, the glass transition temperature (T
g) was measured using a DSC (differential scanning calorimeter) in a nitrogen atmosphere under the condition of a heating rate of 20 ° C./min.
A high value of 266 ° C. was obtained. Using a TGA (thermal balance), a 5% weight loss temperature (the temperature at which the sample weight was reduced by 5% by weight from the initial weight) was measured in a nitrogen atmosphere under the conditions of a heating rate of 10 ° C./min. Measured
A high value of 506 ° C. was obtained. After casting the polymer on a polyimide film to form a film, the relative dielectric constant of the film was measured with an LCR meter 4284A (manufactured by Yokogawa Hewlett-Packard Company) to determine the relative dielectric constant. As a result, the relative dielectric constant of this film was 2.
It was 3. Therefore, it was confirmed that the obtained polymer had excellent heat resistance and low dielectric properties. The obtained polymer was confirmed to have the following structure by IR measurement and the like.

[0036]

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[Where n represents the number of repetitions. ]

[0038]

As described above, by forming a specific bissulfonate compound, a phenylene group-containing polymer having excellent heat resistance, low dielectric properties and processability and being soluble in an organic solvent can be efficiently produced. It has become possible to provide a raw material monomer that can be produced well, stably, and at low cost. Moreover, the effect that the phenylene group-containing polymer synthesized using the bissulfonate compound of the present invention was also excellent in transparency was obtained.

[Brief description of the drawings]

FIG. 1 is a chart showing an IR spectrum of the compound obtained in Example 1.

FIG. 2 is a chart showing an H-NMR spectrum of the compound obtained in Example 1.

FIG. 3 is a chart showing an IR spectrum of the compound obtained in Example 2.

FIG. 4 is a chart showing an H-NMR spectrum of the compound obtained in Example 2.

FIG. 5 is a chart showing an IR spectrum of the compound obtained in Example 3.

FIG. 6 is a chart showing an H-NMR spectrum of the compound obtained in Example 3.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] 1. A bissulfonate compound represented by the following general formula (I). Embedded image [In the formula (I), R ¹ and R ² represent an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, or an aryl group represented by the following general formula (II), R ³ , R ⁴ , R ⁵ , and R ⁶ Is
A hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, and R ⁷ is an aryl group represented by the following general formula (III),
To 3 fluoroalkyl group, R ⁸ represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 3 carbon atoms each, R ¹ and R ^2, R ³ and R ⁴ and R ⁵ and R ^6,
M may be the same or different, and m is an integer of 1 to 5. [Chemical formula 2] [In the formula (II), R ⁹ represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 3 carbon atoms. [Chemical formula 3] [In the formula (III), R ¹⁰ represents a hydrogen atom, a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms. ]