JP7004913B2 - New alicyclic diol compound - Google Patents

Description

The present invention relates to a novel alicyclic diol compound.

An alicyclic diol compound is used as a resin raw material for a polyester resin. However, industrially available alicyclic diol compounds include 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol and 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A). 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 resin raw material and a modifier for a polyester resin, and a novel alicyclic diol compound as a resin raw material such as an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin and a polymethacrylic acid ester resin. do.

As a result of diligent studies to achieve the above problems, the present inventors have found that an alicyclic diol compound having a unique structure is a compound not described in the literature, and is a resin raw material and modifier for polyester resin, epoxy resin, and polyurethane resin. , Polyacrylic acid ester resin, Polymethacrylic acid ester resin, and other resin raw materials have been found to be useful, and the present invention has been completed based on such findings.

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

［式中、Ｒ^１は、同一又は異なって、メチル基又はエチル基を示す。］
で表される、脂環式ジオール化合物。 [Item 1]
General formula (1)

[In the formula, R ¹ represents a methyl group or an ethyl group, which is the same or different. ]
An alicyclic diol compound represented by.

[Item 2]
Item 2. The alicyclic diol compound according to Item 1, wherein the two R ^1s are the same and are a methyl group or an ethyl group.

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

It is an IR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) obtained in Example 1. ^{1 1} H-NMR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) obtained in Example 1. ¹³ C-NMR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) obtained in Example 1. 6 is an IR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) obtained in Example 2. 2 is a ¹ H-NMR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) obtained in Example 2. ¹³ C-NMR spectrum of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) obtained in Example 2.

［式中、Ｒ^１は、同一又は異なって、メチル基又はエチル基を示す。］
で表される、脂環式ジオール化合物である。 The novel alicyclic diol compound of the present invention has the following general formula (1).

[In the formula, R ¹ represents a methyl group or an ethyl group, which is the same or different. ]
It is an alicyclic diol compound represented by.

In the general formula (1), it is recommended that R ¹ is the same or different and is a methyl group or an ethyl group, and preferably R ¹ is the same.

More specifically, 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) and 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) can be mentioned. ..

［式中、Ｒ^１は、同一又は異なって、メチル基又はエチル基を示す。］ The novel alicyclic diol compound of the present invention is produced, for example, as shown in the following reaction formula.
(Reaction formula)

[In the formula, R ¹ represents a methyl group or an ethyl group, which is the same or different. ]

Specifically, the method for producing a novel alicyclic diol compound of the present invention comprises 2,2-bis (4-oxocyclohexyl) propane of the general formula (2) and trimethylol represented by the general formula (3). This is a method for acetalizing a compound.

As the 2,2-bis (4-oxocyclohexyl) propane of the general formula (2), a commercially available product, a reagent, or a product prepared by a known synthetic method can be used. For example, a method of oxidizing industrially available 2,2-bis (4-hydroxycyclohexyl) propane (for example, "Ricabinol HB" manufactured by NEW JAPAN CHEMICAL CO., LTD.) To form a diketone (Japanese Patent Laid-Open No. 5-025080). A method according to the method described in Production Example 1 of Japanese Patent Publication No. 1) is exemplified.

Further, as another method, a method for producing 2,2-bis (4-oxocyclohexyl) propane by dehydrogenating 2,2-bis (4-hydroxycyclohexyl) propane is known. Example 2) of Japanese Patent Publication No. 8-0533386.

The trimethylol compound represented by the general formula (3) is specifically trimethylolethane (R ¹ = methyl group) or trimethylolpropane (R ¹ = ethyl group). Commercial products and reagents can be used for both trimethylolethane and trimethylolpropane.

The alicyclic diol compound represented by the general formula (1) of the present invention is a 2,2-bis (4-oxocyclohexyl) propane represented by the general formula (2) and a trimethylol compound represented by the general formula (3). Can be easily obtained by performing an acetalization reaction in the presence of an acid catalyst and a solvent.

Examples of the acid catalyst include protonic acid and Lewis acid. Examples of the protonic acid include inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, strongly acidic ion exchange resins and superstrong acids. Examples thereof include cation exchange resins such as sex ion exchangeable resins. Lewis acids include boron trifluoride diethyl AEL complex, aluminum trifluoride, iron (III) chloride, zinc chloride, titanium tetrachloride, tin (II) chloride, tin (IV) chloride, white clay, active white clay, molecular sieves, etc. Can be mentioned. Each of these acid catalysts may be used alone or in combination of two or more.

The amount of the acid catalyst used is usually 0.001 to 20% by weight, preferably 0.05 to 15% by weight, still more, relative to 2,2-bis (4-oxocyclohexyl) propane of the general formula (2). It is preferably in the range of 0.5 to 10% by weight.

During the acetalization reaction, the trimethylol compound represented by the general formula (3) is usually 1.0 with respect to 1 mol of the keto group of 2,2-bis (4-oxocyclohexyl) propane of the general formula (2). ~ 2.0, preferably 1.02 to 1.5 mol is used.

The reaction temperature is in the range of 50 to 200 ° C., preferably 60 to 150 ° C., more preferably 60 to 120 ° C. from the viewpoint of improving the reaction rate and suppressing the formation of by-products. The reaction may be under normal pressure, pressure or reduced pressure. Further, the reaction atmosphere may be either under the atmosphere or under the atmosphere of the inert gas.

As the acetalization progresses, water is by-produced, and this water inhibits the acetalization. Therefore, it is preferable to remove the water from the system. The removal of this by-produced water is not particularly limited as long as it is a solvent that does not inhibit the reaction, and total reflux dehydration is performed using a solvent such as methylene chloride, n-hexane, isohexane, cyclohexane, toluene, or xylene as an entrainer. It can be carried out by a known method for separating water. Since the starting materials of the general formulas (2) and (3) are solid at room temperature, these entrainers are preferably added from the start of the reaction in terms of operability. It is preferable that these entrainers are returned to the system after removing water by total reflux dehydration.

The amount of the solvent used is not particularly limited, but is, for example, 100 to 2000 parts by weight, preferably 500 to 1000 parts by weight, based on 100 parts by weight of 2,2-bis (4-oxocyclohexyl) propane of the general formula (2). Is the range of.

After the completion of the acetalization reaction, the obtained crude alicyclic diol compound solution contains an acid catalyst used as a catalyst. The removal of the acid catalyst is usually carried out by a neutralization treatment using a base. Examples of the base used include carbonates such as sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, calcium carbonate and magnesium carbonate, and metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Hydroxide can be mentioned. Among these, carbonates such as sodium carbonate and sodium hydrogen carbonate are preferable. The amount of the base used is, for example, in the range of 1 to 3 equivalents with respect to the acid catalyst used in the reaction, but a large excess can also be used.

After neutralization with a base, a high-purity alicyclic diol compound containing no acid catalyst can be obtained by separation and purification means such as filtration, concentration, extraction, washing, crystallization, column chromatography, etc., or a combination thereof, if necessary. Obtainable.

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 alicyclic diol compound were carried out by the following methods. Reagents were used for compounds not specifically mentioned.

<Compounds used>
2,2-Bis (4-oxocyclohexyl) propane: Made by Tokyo Chemical Industry Co., Ltd. Trimethylolethane: Made by Tokyo Chemical Industry Co., Ltd. Trimethylolpropane: 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-2010
Column: Agilent Technologies, Inc. DB-1 30mx 0.25mm x 0.25μm
Column temperature: 100 to 300 ° C (heating rate 10 ° C / min)
Injection temperature / detector temperature: 305 ° C / 305 ° C
Detector: FID
Carrier gas: Helium gas flow rate: 1.08 ml / min
Sample: 1 wt% acetone solution injection volume: 1 μl

<Melting point>
Using a micro melting point measuring instrument (MP type) manufactured by Yanaco Technical Science Co., Ltd., measure from a temperature about 5 ° C lower than the expected melting point to a temperature rise rate of 1 ° C / min, and visually from the beginning of melting of the sample solid. The temperature until complete melting was measured.

<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 (300 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]
(Manufacturing of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal))
At room temperature, 11.8 g (0.05 mol) of 2,2-bis (4-oxocyclohexyl) propane and 14.4 g (0.12 mol) of trimethylolethane were placed in a 500 ml 4-necked flask equipped with a water separator with a reflux cooling tube. ), 0.59 g of p-toluenesulfonic acid monohydrate and 100 ml of toluene were charged, the system was replaced with nitrogen, the temperature was raised, and the mixture was stirred for 4 hours while azeotropically dehydrating under reflux with toluene. After completion of the reaction, the crystals were precipitated when cooled to room temperature. The reaction solution in which the crystals were precipitated was neutralized with a saturated aqueous sodium carbonate solution as it was, and then the precipitated crystals were filtered. The obtained crystals were washed with toluene and water and then dried to obtain 20.2 g of a crude alicyclic diol compound (isolation yield 91.8%). The obtained crude product was recrystallized from toluene to obtain 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) having a purity of 97.4 GC area%. The melting point was in the range of 175 to 176 ° C.

The IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the obtained 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) were measured. It is shown in FIGS. The peak near 1.71 ppm in the ¹ H-NMR spectrum is the peak of impurities. The peak near 77 ppm in the ¹³ C-NMR spectrum is the peak of deuterated chloroform as a solvent.

IR (cm ^-1 ): 3613, 3390, 2944, 2872, 1468, 1442, 1099, 1054, 1040, 1016, 992, 958, 911

^{1 1} H-NMR (300 MHz, ppm): 0.73 (s, 6H), 0.82 (s, 6H), 1.14-1.18 (m, 4H), 1.20-1.32 (m) , 4H), 1.39-1.42 (m, 2H), 1.54-1.56 (m, 4H), 1.90-1.92 (m, 2H), 1.97-2.00 (M, 2H), 2.60-2.62 (m, 2H), 3.55-3.57 (d, 2H), 3.65-3.70 (m, 10H)

¹³ C-NMR (75MHz, ppm): 17.7, 20.8, 22.6, 22.7, 29.0, 34.9, 36.4, 36.6, 43.5, 65.6 65.8, 66.2, 98.0

[Example 2]
(Manufacturing of 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal))
The same procedure as in Example 1 was carried out except that 16.1 g (0.12 mol) of trimethylolpropane was used instead of trimethylolethane, and 16.2 g of a crude alicyclic diol compound (isolation yield 69.2%) was used. ) Was obtained. The obtained crude product was recrystallized from toluene to obtain 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) having a purity of 98.2 GC area%. The melting point was in the range of 170-171.5 ° C.

The IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the obtained 2,2-bis (4-oxocyclohexyl) propane-bis (trimethylolpropane acetal) were measured. It is shown in FIGS. 4 to 6. The peak near 1.63 ppm and the peak around 2.36 ppm in the ¹ H-NMR spectrum are the peaks of impurities. The peak near 77 ppm in the ¹³ C-NMR spectrum is the peak of deuterated chloroform as a solvent.

IR (cm ^-1 ): 3428, 2944, 2866, 1474, 1445, 1099, 1060, 1031, 974, 917, 896

^{1 1} H-NMR (300 MHz, ppm): 0.73 (m, 6H), 0.84 (t, 6H), 1.10-1.17 (m, 4H), 1.261.32 (m, 8H) ), 1.35-1.41 (m, 2H), 1.54-1.56 (m, 4H), 1.73-1.76 (m, 2H), 1.97-2.00 (m) , 2H), 2.58-2.60 (m, 2H), 3.59-3.72 (m, 8H), 3.76-3.77 (m, 4H)

¹³ C-NMR (75MHz, ppm): 20.7, 20.8, 22.7, 22.8, 24.0, 29.0, 36.4, 36.6, 37.0, 43.5, 63.3, 64.5, 64.7, 98.1

The novel alicyclic diol compound of the present invention can be used as a resin raw material and a modifier for polyester resin, and as a resin raw material for epoxy resin, polyurethane resin, polyacrylic acid ester resin, polymethacrylic acid ester resin and the like.

Claims (1)

General formula (1)

[In the formula, R ¹ represents a methyl group or an ethyl group, which is the same or different. ]
An alicyclic diol compound represented by.

Images