JP7014962B2 - New cyclic diol compound - Google Patents

Description

The present invention relates to novel cyclic diol compounds.

Various diol compounds are known as resin raw materials for polyester resins and polycarbonate resins. However, industrially available cyclic diol compounds include 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol and 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A). However, there are few types (Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 5-310900 Japanese Patent Application Laid-Open No. 2003-048966

An object of the present invention is to provide a novel cyclic diol compound. The novel cyclic diol compound is useful as a resin raw material such as a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, and a polymethacrylic acid ester resin, and a resin modifier.

As a result of diligent studies to achieve the above problems, the present inventors have found that a cyclic diol compound having a unique structure is a compound not described in the literature, and is a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, or a polyacrylic acid ester. We have found that it is useful as a resin raw material such as a resin and a polymethacrylic acid ester resin and a resin modifier, and have completed the present invention based on such findings.

That is, the present invention provides a novel cyclic diol compound whose gist is as follows.

［式中、Ｒ¹～Ｒ^１２は、同一又は異なって、それぞれ、水素原子若しくは置換基を有していてもよい炭素数１～１０のアルキル基又は置換基を有していてもよい炭素数６～１０の芳香族基を示す。また、Ｒ^１～Ｒ^１２のうち、２つの基が互いに結合して２価の基を形成していてもよい。］
で表される環式ジオール化合物。 [Item 1]
General formula (1)

[In the formula, R ¹ to R ¹² are the same or different, and may have an alkyl group or a substituent having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, respectively. Shows 6-10 aromatic groups. Further, two groups of R ¹ to R ¹² may be bonded to each other to form a divalent group. ]
Cyclic diol compound represented by.

［式中、Ｒ¹～Ｒ^１２は、同一又は異なって、それぞれ、水素原子若しくは置換基を有していてもよい炭素数１～１０のアルキル基又は置換基を有していてもよい炭素数６～１０の芳香族基を示す。また、Ｒ^１～Ｒ^１２のうち、２つの基が互いに結合して２価の基を形成していてもよい。］
で表される環式ジオール化合物の、ポリエステル樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂又はポリメタクリル酸エステル樹脂の樹脂原料としての使用方法。 [Item 2]
General formula (1)

[In the formula, R ¹ to R ¹² are the same or different, and may have an alkyl group or a substituent having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, respectively. Shows 6-10 aromatic groups. Further, two groups of R ¹ to R ¹² may be bonded to each other to form a divalent group. ]
A method for using the cyclic diol compound represented by (1) as a resin raw material for a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin or a polymethacrylic acid ester resin.

［式中、Ｒ¹～Ｒ^１２は、同一又は異なって、それぞれ、水素原子若しくは置換基を有していてもよい炭素数１～１０のアルキル基又は置換基を有していてもよい炭素数６～１０の芳香族基を示す。また、Ｒ^１～Ｒ^１２のうち、２つの基が互いに結合して２価の基を形成していてもよい。］
で表される環式ジオール化合物からなる、ポリエステル樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂又はポリメタクリル酸エステル樹脂の樹脂改質剤。 [Item 3]
General formula (1)

[In the formula, R ¹ to R ¹² are the same or different, and may have an alkyl group or a substituent having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, respectively. Shows 6-10 aromatic groups. Further, two groups of R ¹ to R ¹² may be bonded to each other to form a divalent group. ]
A resin modifier for a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, or a polymethacrylic acid ester resin, which comprises a cyclic diol compound represented by.

The novel cyclic diol compound of the present invention can be used as a resin raw material or a resin modifier such as a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, and a polymethacrylic acid ester resin.

Of 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-bis (2-hydroxyethyloxy) -1,1'-binaphthyl obtained in Example 1. IR spectrum. Of 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-bis (2-hydroxyethyloxy) -1,1'-binaphthyl obtained in Example 1. ^{1 1} H-NMR spectrum. Of 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-bis (2-hydroxyethyloxy) -1,1'-binaphthyl obtained in Example 1. ¹³ C-NMR spectrum.

［式中、Ｒ¹～Ｒ^１２は、同一又は異なって、それぞれ、水素原子若しくは置換基を有していてもよい炭素数１～１０のアルキル基又は置換基を有していてもよい炭素数６～１０の芳香族基を示す。また、Ｒ^１～Ｒ^１２のうち、２つの基が互いに結合して２価の基を形成していてもよい。］
で表される、環式ジオール化合物である。 The novel cyclic diol compound of the present invention has the following general formula (1).

[In the formula, R ¹ to R ¹² are the same or different, and may have an alkyl group or a substituent having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, respectively. Shows 6-10 aromatic groups. Further, two groups of R ¹ to R ¹² may be bonded to each other to form a divalent group. ]
It is a cyclic diol compound represented by.

In the general formula (1), the alkyl group of the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R ¹ to R ¹² is not particularly limited, but is, for example, linear or branched. Examples thereof include a chain-like alkyl group having 1 to 10 carbon atoms. Specific examples thereof include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group and hexyl group. Of these, a methyl group, an ethyl group, an isobutyl group and a tert-butyl group are preferable.

In the general formula (1), the aromatic group of the aromatic group having 6 to 10 carbon atoms which may have a substituent represented by R ¹ to R ¹² is not particularly limited, but for example, a phenyl group and the like. o-tolyl group, m-tolyl group, p-tolyl group, 2,3-kisilyl group, 2,4-kisilyl group, 2,5-kisilyl group, 2,6-xsilyl group, 3,4-xsilyl group, Examples thereof include aromatic groups such as 3,5-xylyl group, 3,6-xylyl group, 4,6-xylyl group, mesityl group and naphthyl group. Of these, a phenyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group are preferable.

Further, in the general formula (1), of R ¹ to R ¹² , the divalent group in which two groups are bonded to each other is not particularly limited, and examples thereof include a benzene ring and a tetralin ring.

上記式（１）～式（３）において、Ｒ¹～Ｒ^１２は、同一又は異なって、それぞれ、水素原子若しくは置換基を有していてもよい炭素数１～１０のアルキル基又は置換基を有していてもよい炭素数６～１０の芳香族基を示す。また、Ｒ^１～Ｒ^１２のうち、２つの基が互いに結合して２価の基を形成していてもよい。 The novel cyclic diol compound of the present invention is produced, for example, as shown in the following reaction formula.
(Reaction formula)

In the above formulas (1) to (3), R ¹ to R ¹² have the same or different alkyl groups or substituents having 1 to 10 carbon atoms which may have hydrogen atoms or substituents, respectively. It shows an aromatic group having 6 to 10 carbon atoms which may have. Further, two groups of R ¹ to R ¹² may be bonded to each other to form a divalent group.

Specifically, in the method for producing a novel cyclic diol compound of the present invention, a 1,1'-bi-2-naphthol derivative represented by the general formula (2) is hydrogenated in the presence of a noble metal catalyst. , A production method in which an octahydro-2,2'-dihydroxy-1,1'-binaphthyl derivative represented by the general formula (3) is prepared and then subjected to a hydroxyethyl etherification reaction using ethylene carbonate in the presence of a basic compound. Is.

Examples of the hydrogenation reaction of the 1,1'-bi-2-naphthol derivative represented by the general formula (2) include methods according to those described in JP-A-2005-126433.

The hydroxyethyl etherification reaction of the octahydro-2,2'-dihydroxy-1,1'-binaphthyl derivative represented by the general formula (3) is described in JP-A-2014-227388 and JP-A-2015-168658. Examples thereof include methods according to those described in the publication.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this example, various measurements of the cyclic diol compound were carried out by the following methods. Reagents were used for compounds not specifically mentioned.

<Compounds used>
1,1'-B-2-Naftor: Made by Tokyo Chemical Industry Co., Ltd.

<Analysis by gas chromatography (GC)>
The purity (GC area%) of the alicyclic diol compound was measured by gas chromatography (GC).

[Measurement condition]
Equipment: Shimadzu GC-2014
Column: Agilent Technologies, Inc. DB-1 30mx 0.25mm x 0.25μm
Column temperature: 100 to 320 ° C (heating rate 15 ° C / min)
Injection temperature / detector temperature: 300 ° C / 325 ° C
Detector: FID
Carrier gas: Helium gas flow rate: 1.13 ml / min
Sample: 1 mass% acetone solution injection volume: 1 μl

<Infrared absorption spectrum (IR spectrum)>
The IR spectrum of the alicyclic diol compound was carried out by an ATR method (attenuated total reflection method) using an infrared spectrophotometer (Spectrum400 manufactured by PerkinElmer Japan Co., Ltd.).

<Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)>
¹ H-NMR of the alicyclic diol compound was carried out by ¹ H-NMR (500 MHz) measurement using a nuclear magnetic resonance apparatus (DRX-500 manufactured by Bruker) after dissolving in deuterated chloroform.

<Carbon Nuclear Magnetic Resonance Spectrum ( ¹³ C-NMR)>
The alicyclic diol compound ¹³ C-NMR was measured by ¹³ C-NMR (125.8 MHz) using a nuclear magnetic resonance apparatus (DRX-500 manufactured by Bruker) after dissolving it in deuterated chloroform.

[Example 1]
Add 45.0 g (0.16 mol) of 1,1'-bi-2-naphthol, 33.0 g of ₅ % Pd / Al _2O and 105 g of ethanol to a 500 mL autoclave with an electromagnetic stirrer, and add hydrogen while stirring. The reaction was carried out at a pressure of 5 MPa and a reaction temperature of 130 ° C. for 5 hours. After cooling the reaction mixture to room temperature, the catalyst was removed by filtration. The obtained filtrate was gradually increased in temperature from room temperature at normal pressure to distill off ethanol, and then purified on a silica gel column (developing solvent: hexane / diethyl ether = 2/1) to have a purity of 99.6 GC area%. 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-dihydroxy-1,1'-binaphthyl were obtained.

5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-in a 300 ml glass reactor equipped with a stirrer, nitrogen blow tube, thermometer and condenser. 40.0 g (0.14 mol) of dihydroxy-1,1'-binaphthyl, 10.0 g (0.109 mol) of toluene, 18.6 g (0.211 mol) of ethylene carbonate and 2.0 g (0.008 mol) of triphenylphosphine. Was charged and stirred at 115 ° C. for 11 hours to complete the reaction. After completion of the reaction, toluene and a 15% by mass sodium hydroxide aqueous solution were added to the reaction crude product, and the mixture was stirred and washed at 85 ° C. for 1 hour and then allowed to stand to separate the lower layer (aqueous layer). Similarly, the washing operation was performed twice, and then the organic layer was further washed with water three times. The obtained organic layer was distilled off under reduced pressure, and crude 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-bis (2-hydroxyethyloxy) -1, Obtained 1'-binaphthyl. By recrystallizing and purifying the crude product obtained using ethyl acetate, the purity is 99.4 GC area%, 5,5', 6,6', 7,7', 8,8'-octahydro-2,2. '-Bis (2-hydroxyethyloxy) -1,1'-binaphthyl was obtained.

IR spectra of the obtained 5,5', 6,6', 7,7', 8,8'-octahydro-2,2'-bis (2-hydroxyethyloxy) -1,1'-binaphthyl, ^{1 1} H-NMR spectrum and ¹³ C-NMR spectrum were measured. It is shown in FIGS. The peak near 7.25 ppm in the ¹ H-NMR spectrum and the peak near 77 ppm in the ¹³ C-NMR spectrum are peaks derived from deuterated chloroform as a solvent.

IR (cm ^-1 ): 3393, 2923, 2855, 1591, 1474, 1450, 1255, 1236, 1076, 1036, 953, 797

^{1 1} H-NMR (500MHz, ppm): 1.70 (m, 8H), 2.16 (m, 4H), 2.32 (s, 2H), 2.76 (t, 4H), 3.61 ( m, 2H), 3.67 (m, 2H), 3.93 (m, 2H), 4.08 (m, 2H), 6.79 (d, 2H), 7.04 (d, 2H)

¹³ C-NMR (125.8 MHz, ppm): 23.0, 23.1, 273, 29.3, 61.2, 70.8, 111.4, 126.7, 128.9, 130. 9, 136.8, 152.9

The novel cyclic diol compound of the present invention can be used as a resin raw material such as a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin and a polymethacrylic acid ester resin, or as a resin modifier.

Claims (1)

General formula (1)

[In the formula, R ¹ to R ¹² represent a hydrogen atom or a methyl group, an ethyl group, an isobutyl group, and a tert-butyl group, respectively, which are the same or different. ]
Cyclic diol compound represented by.

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