JP4678195B2 - Phenanthrenequinone derivative and method for producing the same - Google Patents

Description

  The present invention relates to a novel 9,10-phenanthrenequinone derivative, a polymer material, a resin material, a raw material for a resist material, for example, a raw material for a thermoplastic resin such as polycarbonate or polyarylate, or a thermosetting resin such as an epoxy resin. The present invention relates to a novel compound useful as a raw material, a curing agent, a modifier, etc., or a compound for molecular resist.

Various bisphenols are used as raw materials for thermoplastic resins such as polycarbonate and polyarylate, raw materials for thermosetting resins such as epoxy resins, curing agents, modifiers, etc., but heat resistance, water resistance, chemical resistance Further improvements in various characteristics such as electrical characteristics and mechanical characteristics are demanded. Further, it has been reported that a bisphenol compound is useful as a base compound of a resist material (see Non-Patent Document 1). However, it cannot be said that the conventional bisphenol compound has sufficient heat resistance.
Polymer Preprints, Japan Vol.53, No.2, 1Pc117

    An object of the present invention is to provide a bisphenol compound used as a raw material for polymer materials and resin materials and a raw material for resist materials.

As a result of intensive studies, the present inventors have found that a bisphenol compound derived from 9,10-phenanthrenequinone can solve the above problems, and have completed the present invention.
That is, the present invention relates to the following compounds [1] to [2] and a method for producing [3].

（式（１）中、
Ｒ^１、Ｒ^２は、炭素数１〜６のアルキル基であり；
ｍ０、ｎ０は１〜３の整数であり；
ｍ１、ｎ１は０〜３の整数であり；
２≦ｍ０＋ｍ1≦５ 、２≦ｎ０＋ｎ1≦５の条件を満たす。但し、複数個のＲ^１、Ｒ^２は、各々同一でも異なっていても良い。） [1] A compound represented by the general formula (1).

(In the formula (1),
R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms;
m0 and n0 are integers of 1 to 3;
m1 and n1 are integers of 0 to 3;
The condition of 2 ≦ m0 + m1 ≦ 5 and 2 ≦ n0 + n1 ≦ 5 is satisfied. However, the plurality of R ¹ and R ² may be the same or different. )

（式（２）中、ｐ１、ｐ２、ｑ１、ｑ２は０または１の整数である。） [2] The compound according to [1] represented by the general formula (2).

(In formula (2), p1, p2, q1, and q2 are 0 or an integer of 1.)

（式（１）中、
Ｒ^１、Ｒ^２は、炭素数１〜６のアルキル基であり；
ｍ０、ｎ０は１〜３の整数であり；
ｍ１、ｎ１は０〜３の整数であり；
２≦ｍ０＋ｍ1≦５ 、２≦ｎ０＋ｎ1≦５の条件を満たす。但し、複数個のＲ^１、Ｒ^２は、各々同一でも異なっていても良い。） [3] A process for producing a compound of the general formula (1), comprising reacting 9,10-phenanthrenequinone and a phenol compound in the presence of thioacetic acid or β-mercaptopropionic acid, and hydrochloric acid or sulfuric acid.

(In the formula (1),
R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms;
m0 and n0 are integers of 1 to 3;
m1 and n1 are integers of 0 to 3;
The condition of 2 ≦ m0 + m1 ≦ 5 and 2 ≦ n0 + n1 ≦ 5 is satisfied. However, the plurality of R ¹ and R ² may be the same or different. )

  The bisphenol compound of the present invention is a raw material for polymer materials and resin materials, a raw material for resist materials, for example, a raw material for thermoplastic resins such as polycarbonate and polyarylate, a raw material for thermosetting resins such as epoxy resins, a curing agent, a modified material. It is useful as a raw material for a quality agent or a molecular resist compound.

The compound of the present invention (hereinafter referred to as compound (A)) is a compound represented by the general formula (1).
In the compound (A), the number and position of substituents (alkyl group and hydroxyl group) of two phenyl groups may be different, but are preferably the same.

In the compound (A), R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms. Specific examples include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl and the like.

Among these, R ¹ and R ² are preferably methyl groups. n1 and m1 are preferably 0 to 2.
Both n0 and m0 indicating the number of hydroxyl groups are preferably 1, and the substitution position is preferably position number 4 of the benzene ring bonded to the phenanthrene ring.
The substitution positions of R ¹ and R ² are preferably position numbers 2 and / or 5 of the benzene ring bonded to the phenanthrene ring.
The compound (A) is preferably a compound represented by the general formula (2).

  The compound of the general formula (1) of the present invention can be produced, for example, by reacting 9,10-phenanthrenequinone and a phenol compound in the presence of thioacetic acid or β-mercaptopropionic acid, and hydrochloric acid or sulfuric acid.

As the phenol compound used in the present invention, phenol, resorcinol, catechol, pyrogallol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- Examples include xylenol, 2,3,5-trimethylphenol, and 2,3,6-trimethylphenol.
In particular, phenol, resorcinol, catechol, pyrogallol, o-cresol, and 2,6-xylenol are preferable.
One type or two or more types can be used as the phenol compound.

In the reaction, 2 mol to excess of a phenol compound and 0.001 to 1 mol of thioacetic acid or β-mercaptopropionic acid and hydrochloric acid or sulfuric acid are used with respect to 1 mol of 9,10-phenanthrenequinone and 20 to 70 to 120 ° C. The reaction proceeds advantageously by reacting for about 20 minutes.
The end point of the reaction can be determined as the end point of the reaction by tracking the remaining amount of 9,10-phenanthrenequinone by gas chromatography and the peak area indicating the remaining amount no longer decreases.
After completion of the reaction, for example, methanol or isopropyl alcohol is added to the reaction solution, and the mixture is heated to 60 ° C. and stirred for 1 hour. Next, pure water is added to precipitate a reaction product, which is cooled to room temperature and filtered. Can be used to separate a solid containing the compound of general formula (1) as a main component. The obtained solid is filtered and dried, and then the target compound is obtained.
The compound of General formula (2) of this invention can be manufactured similarly to the compound of General formula (1) by using 1 or more types chosen from phenol, o-cresol, and 2, 6- xylenol as a phenol compound.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not particularly limited to these examples.
In addition, the evaluation method of a compound is as follows.
<Measurement of glass transition temperature>
Using DSC / TA-50WS manufactured by Shimadzu Corporation, about 10 mg of a sample was put in an aluminum non-sealed container and heated to 250 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen gas (30 ml / min) airflow. After rapidly cooling the aluminum non-sealed container, DSC measurement was performed by heating again to 250 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen gas (30 ml / min) stream. At that time, the temperature at the midpoint of the region where the discontinuous portion appears in the baseline (where the specific heat has changed to half) is defined as the glass transition point (Tg), and the temperature indicating the minimum value of the endothermic peak is defined as the melting point (Tm). did.

<Example 1>
In a container with a volume of 100 ml equipped with a stirrer, a condenser and a burette, 10.4 g (0.05 mol) of 9,10-phenanthrenequinone (Across Organics) and 18.8 g (0.2 mol) of phenol (Kanto Chemical Industries) ), 5 ml of β-mercaptopropionic acid and 5 ml of 95% sulfuric acid were added, and the reaction solution was stirred at 85 ° C. for 6 hours to complete the reaction. After completion of the reaction, 50 g of methanol or isopropyl alcohol was added to the reaction solution and heated to 60 ° C., and stirring was continued for 1 hour. Next, 90 g of pure water was added to precipitate the reaction product, cooled to room temperature, and then filtered to separate. The obtained solid was filtered and dried, and then the target compound (1-1) was obtained. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of formula (1-1). It was 119 degreeC when the glass transition temperature of the target compound (1-1) was measured, and it did not have melting | fusing point.
¹ H-NMR: (400 MHz, d-DMSO, internal standard TMS)
δ (ppm) 9.4 (2H 2 O— H ), 8.2 to 7.3 (8H Ph H —Ph H ), 6.6 (8H Ph— H )

<Example 2>
The same procedure as in Example 1 was carried out except that 21.6 g (0.2 mol) of o-cresol was used and 5 ml of β-mercaptopropionic acid was replaced with 3 ml of thioacetic acid to obtain the target compound (1-2). It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of formula (1-2). It was 120 degreeC when the glass transition temperature of the target compound (1-2) was measured, and it did not have melting | fusing point.
¹ H-NMR: (400 MHz, d-DMSO, internal standard TMS)
δ (ppm) 9.4 (2H 2 O— H ), 8.2 to 6.7 (8H Ph H —Ph H ), 6.7 to 6.4 (6H Ph— H ), 2.0 (6H Ph -C H ₃₎

<Example 3>
The same procedure as in Example 1 was carried out except that phenol was replaced with 24.4 g (0.2 mol) of 2,6-xylenol to obtain the target compound (1-3). It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of formula (1-3). It was 130 degreeC when the glass transition temperature of the target compound (1-3) was measured, and melting | fusing point was 282 degreeC.
¹ H-NMR: (400 MHz, d-DMSO, internal standard TMS)
δ (ppm) 8.3 (2H 2 O— H ), 8.2 to 6.7 (8H Ph H —Ph H ), 6.3 (4H Ph— H ), 2.0 (12H Ph—C H ₃ )

Claims (3)

A compound represented by the general formula (1).

(In the formula (1),
R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms;
m0 and n0 are integers of 1 to 3;
m1 and n1 are integers of 0 to 3;
The condition of 2 ≦ m0 + m1 ≦ 5 and 2 ≦ n0 + n1 ≦ 5 is satisfied. However, the plurality of R ¹ and R ² may be the same or different. ) The compound of Claim 1 shown by General formula (2).

(In formula (2), p1, p2, q1, and q2 are 0 or an integer of 1.) A process for producing a compound of the general formula (1), comprising reacting 9,10-phenanthrenequinone and a phenol compound in the presence of thioacetic acid or β-mercaptopropionic acid, and hydrochloric acid or sulfuric acid.

(In the formula (1),
R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms;
m0 and n0 are integers of 1 to 3;
m1 and n1 are integers of 0 to 3;
The condition of 2 ≦ m0 + m1 ≦ 5 and 2 ≦ n0 + n1 ≦ 5 is satisfied. However, the plurality of R ¹ and R ² may be the same or different. )