JP2002020348A - Method for producing diol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing bis(2-hydroxyethyl)5- hydroxyisophthalate in a high purity and in a high yield. SOLUTION: This method for producing bis(2-hydroxyethyl)5- hydroxyisophthalate by thermally reacting a 5-hydroxyisophthalic acid compound represented by the general formula (1) (R is H or an alkyl) with ethylene glycol, characterized by using the ethylene glycol in an amount of 5 to 200 fold moles that of the 5-hydroxyisophthalic acid compound in the presence of a catalyst such as a metal in the group 1 to the group 8 in the periodic table, a compound of the metal, an organic acid, a solid acid, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel process for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate.

[0002]

2. Description of the Related Art An example has been reported in which dimethyl terephthalate and ethylene glycol are demethanolized in the presence of a zinc acetate catalyst to obtain bis (2-hydroxyethyl) terephthalate (Czechoslovak Patent (CS) 1808).
No. 54). However, there is no known example of producing bis (2-hydroxyethyl) 5-hydroxyisophthalate from 5-hydroxyisophthalic acid or dialkyl 5-hydroxyisophthalate and ethylene glycol.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide 5-
An object of the present invention is to provide a method for economically producing bis (2-hydroxyethyl) 5-hydroxyisophthalate from a hydroxyisophthalic acid compound.

[0004]

That is, the present invention provides a method of formula (1)

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group.) A bis (2-hydroxyethyl) 5-hydroxyisophthalate is obtained by heat-treating a 5-hydroxyisophthalic acid compound represented by the following formula and ethylene glycol in the presence of a catalyst. At this time, the present invention relates to a method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate, wherein ethylene glycol is used in a molar amount of 5 to 200 times the amount of the 5-hydroxyisophthalic acid compound.

[0005] The reaction of the present invention is shown by the following scheme.

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group.) A 5-hydroxyisophthalic acid compound represented by the formula (1) and ethylene glycol (abbreviated as EG) are subjected to heat treatment using a catalyst to form a dehydrated ester. It is characterized in that bis (2-hydroxyethyl) 5-hydroxyisophthalate (abbreviated as BH5HI) is produced by conversion or transesterification.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the raw material 5-hydroxyisophthalic acid compound represented by the formula (1), when R is a hydrogen atom,
Hydroxyisophthalic acid (hereinafter abbreviated as 5HI)
Can be used as it is or commercially available. When R is an alkyl group in the general formula (1), dialkyl 5-hydroxyisophthalate (hereinafter referred to as DA5
HI) is obtained by esterifying 5-hydroxyisophthalic acid. The alkyl group of the ester portion of DA5HI has 1 to 20 carbon atoms, preferably 1 to 1 carbon atom.
0, more preferably 1 to 4 carbon atoms. DA5HI
Specific examples thereof include dimethyl 5-hydroxyisophthalate, diethyl 5-hydroxyisophthalate, dipropyl 5-hydroxyisophthalate and dibutyl 5-hydroxyisophthalate.

[0007] The other raw material, EG, can be used as it is or purified from commercial products.

When the amount of EG charged to the 5-hydroxyisophthalic acid compound is small, the by-product of the reaction between the 5-hydroxyisophthalic acid compound and the target product, BH5HI, increases. It has been found that by-products are reduced. That is, EG /
The 5-hydroxyisophthalic acid compound is preferably 5- to 200-fold molar, more preferably 10- to 100-fold molar in view of the selectivity and economy of BH5HI, and particularly preferably 2 to 2-fold molar.
It is 0 to 50 times mol. By using 20 mole times or more, the amount of by-products can be suppressed to within several percent. The excess EG is recovered and reused after the reaction.

In the present reaction, the presence of a catalyst is important. The 5-hydroxyisophthalic acid compound itself exhibits an acid-catalyzing effect at a high temperature even in the absence of a catalyst and produces BH5HI, but has a low selectivity and is not practical. As a kind of applicable catalyst, it has been found that a Lewis acid type catalyst which is a metal of Groups 1 to 8 of the periodic table and a metal compound thereof can be widely used. Also, inorganic and organic protonic acids,
It has been found that (hetero) polyacids, solid acids, cation exchange resins and the like also exhibit a catalytic effect.

First, the Lewis acid type catalyst will be described. The form of the catalyst is the metal itself and / or the metal compound. In some cases, these forms are used in a form supported on a carrier (silica, silica alumina, activated carbon, zeolite and others).

Specific types of metals include Cu, Ag, Au of the first group of the periodic table, Zn, Cd, Hg, and the second group of the periodic table.
Group 3 B, Al, Ga, In, Sc, lanthanide-based metals (La, Ce, Sm, Yb, Th, U), Group 4 T
i, Zr, Hf, Ge, Sn, group 5 As, Sb, B
i, Group 6 Mo and W, Group 7 Mn and Re, Group 8 Fe, Co, Ni, Ru, Rh, Pd, Ir and Pt are typical examples. Among these metals, metals of Groups 2 to 8 of the periodic table are preferable. More preferred metals include zinc, tungsten, manganese, titanium, cadmium, iron, scandium and lanthanide rare earths. Particularly preferred metals include zinc, tungsten, manganese, titanium, iron, ytterbium and palladium.

Here, the kind of the metal compound is
Organic complexes such as tilacetonate, hydrofluoric acid, hydrochloric acid, odor
Hydrofluoric acid, hydroiodic acid, sulfuric acid, phosphoric acid, sulfonic acid and
Mineral acid salts such as nitric acid, formic acid, acetic acid, propionic acid, oxalic acid and
Carboxylates such as benzoic acid, methanesulfonic acid, and triflic acid
Fluoromethanesulfonic acid, benzenesulfonic acid and p-
Organic salts such as sulfonic acid salts such as toluenesulfonic acid are listed.
I can do it. More specifically, Zn, Zn (CH_TwoCOC
H_TwoCOCH_Three)_Two, ZnCl_Two, ZnBr_Two, Zn_Three(P
O_Four)_Two, ZnSO_Four, Zn (NO_Three)_Two, Zn (HC
O_Two)_Two, Zn (CH_ThreeCO_Two)_Two, Zn (O_TwoCCO_Two),
CdCl_Two, Cd (CH_ThreeCO_Two)_Two, Cd_Three(PO_Four)_Two,
Cd (CH_TwoCOCH_TwoCOCH_Three)_Two, CdSO_Four, B
F_Three, BCl_Three, BBr_Three, AlCl_Three, AlBr_Three, Ga
Cl_Three, InCl_Three, Sc (CF_ThreeSO_Three)_Three, La (CF
_ThreeSO_Three)_Three, Yb (CF_ThreeSO_Three)_Three, TiO (CH_TwoC
OCH_TwoCOCH_Three)_Two, Ti (CH_ThreeCO_Two)_Four, TiC
l_Four, ZrCl_Four, Hf (CF_ThreeSO_Three)_Four, Ge (CH_ThreeC
O_Two)_Four, GeCl_Four, SnCl_Two, SnCl_Four, SbC
l_Three, Sb (CH_ThreeCO_Two)_Three, Bi (CH_ThreeCO_Two)_Three, 5
(NH_Four)_Two・ 12MoO_Three, WO_Three, H_TwoWO_Four, 5 (NH
_Four)_Two・ 12WO_Three, (NH_Four)₆H_TwoW₁₂O₄₀, Mn, M
n (CH_ThreeCO_Two)_Four, MnCl_Four, MnBr_Two, Mn
(CH_TwoCOCH_TwoCOCH_Three)_Two, Mn (CH_TwoCOCH_Two
COCH_Three)_Three, Mn (CH_TwoCOCH_TwoCOCF_Three)_Two, M
nSO_Four, Mn (HCO_Two)_Two, Mn (C₆H_FiveCO_Two)_Two,
Re, Re (CH_ThreeCO_Two)_Four, Fe, FeCl_Three, Fe
(CH_ThreeCO_Two)_Two, FeC_TwoO_Four, Fe (CH_TwoCOCH
_TwoCOCH_Three)_Two, Fe (CH_TwoCOCH_TwoCOCH_Three)_Three,
Co (CH_ThreeCO_Two)_Two, CoCl_Two, Ni, Ni (CH_Three
CO_Two)_Two, NiCl_Two, Ru (CH_ThreeCO_Two)_Two, RuCl
_Three, Rh / activated carbon, Rh / alumina, Pd, PdC
l _Three, Pd / activated carbon, Pd / alumina, Pd (CH_TwoC
OCH_TwoCOCH_Three)_Two, IrCl_Three, PtCl_Three, Pt
/ Activated carbon, Pt / alumina and the like. These gold
The genus alone and the metal compound may be used in combination of one or more.
I do not care.

[0013] Preferable metal catalysts include zinc, tungsten, manganese and Pd / activated carbon and Pd / alumina as metal-supported catalysts.
Zn (CH ₃ CO ₂ ) ₂ , ZnSO ₄ , Mn (CH ₃ C
O ₂ ) ₂ , WO ₃ , H ₂ WO ₄ , 5 (NH ₄ ) ₂ · 12WO ₃ ,
TiO (CH ₂ COCH ₂ COCH ₃ ) ₂ , FeCl ₃ , Y
b (CF ₃ SO ₃ ) ₃ .

As a protonic acid (Bronsted acid) catalyst
HF, HCl, HBr, HI, H_TwoSO_Four, HNO
_ThreeAnd H_ThreePO_FourMineral acids such as HCO_TwoH, CH_ThreeCO_TwoH,
C_TwoH_FiveCO_TwoH, CF_ThreeCO_TwoH and HO_TwoCCO_TwoH etc.
Aliphatic carboxylic acids, CH_ThreeSO_ThreeH, CF_ThreeSO_ThreeH, C
_TwoH_FiveSO_ThreeH, C₆H_FiveSO_ThreeH and p-CH_ThreeC₆H_FourSO_Three
H and other sulfonic acids. These protic acids
The preferred catalyst is H_TwoSO_Four, HCl, CH_ThreeS
O_ThreeH, CF_ThreeSO_ThreeH, C_TwoH_FiveSO_ThreeH, C₆H _FiveSO_ThreeH
And p-CH_ThreeC₆H_FourSO_ThreeH. Especially preferred
Ino is H_TwoSO_Four, HCl and p-CH_ThreeC₆H_FourSO_ThreeH
It is.

As the (hetero) polyacid catalyst, H ₃ PW
₁₂ O ₄₀ , H ₆ P ₂ W ₁₈ O ₆₂ , H ₇ PW ₁₁ O ₃₉ , H ₇ P (W ₂
O ₇ ) ₆ , H ₄ SiW ₁₂ O ₄₀ , H ₄ TiW ₁₂ O ₄₀ , H ₅ Co
_{W 12 O 4 0, H 5} FeW 12 O 40, H 0.5 Cs 2.5 PW
₁₂ O ₄₀ , H ₂ MoO ₅ , H ₃ PMo ₁₂ O ₄₀ , H ₆ P ₂ Mo _{18
O 62, H 7 PMo 11 O} 39, H 3 PMo 6 W 6 O 40 and H ₄ P
MoW ₁₁ O _{40 and the} like. These may be anhydrides or hydrates. A preferred catalyst among these is H ₃
PW ₁₂ O ₄₀ or H ₄ PMoW ₁₁ O ₄₀ . One or more of these (hetero) polyacid catalysts may be used in combination.

As the solid acid catalyst, silica, alumina,
Examples thereof include silica alumina, zeolite, K-10 (diatomaceous earth manufactured by Nissan Gardler Co., Ltd.), and Daiso gel (silica gel manufactured by Daiso Corporation).

Further, as a cation exchange resin catalyst, a strong acid cation exchange resin (sulfonic acid resin) [trade name: Amberlyst 15, Amber by Rohm & Haas Company]
lite IR-120 and 200, Dowex50, P
ermutitQ, Duolite C-20, Lew
atit S-100, Diaion SKIA, SK
IB] or weakly acidic cation exchange resin (carboxylic acid resin)
[Rohm & Haas product name Amberlite I
RC-50, Lewatit CNO, Permuti
tH-70, Duolite CS-101] and the like.

The amount of the catalyst used is 0.01 to 50 mol% or 0.01 to 50 mol% based on the 5-hydroxyisophthalic acid compound.
It is 50% by weight, preferably 0.05 to 20% by mole, and 0.05 to 20% by weight is practical.

In this reaction, a solvent may be used in addition to EG. Examples of solvents which may be used include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene and durene which can form an azeotropic distillate with water; and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and triethylene. Ethers such as glycol dimethyl ether can be mentioned. The use amount of these additional solvents is usually 1 to 20 times the weight of 5HI.

The reaction temperature varies depending on the reaction conditions, especially the type of catalyst used and the reaction pressure selected. When the catalyst used is a metal, metal compound or solid acid catalyst,
Preferred reaction temperatures are in the range of 130-250 ° C. When the reaction temperature is lower than 130 ° C., the by-product of the monoester intermediate formed from 1 mol of each of the 5-hydroxyisophthalic acid compound and ethylene glycol increases, but the diester BH5HI is converted from the monoester intermediate. The rate of the resulting second esterification reaction is greatly reduced or substantially stopped. If the reaction temperature exceeds 250 ° C., side reactions such as esterification further proceeding from BH5HI, and side reactions including dehydration and etherification of ethylene glycol itself undesirably proceed.

When the catalyst used is a protonic acid or a cation exchange resin, the preferred reaction temperature is between 80 and 15
It is in the range of 0 ° C. Outside the reaction temperature range, the same phenomenon as when the catalyst is a metal compound or a solid acid catalyst occurs, which is not preferable.

If the catalyst used is a (hetero) polyacid catalyst, the preferred reaction temperature is in the range from 80 to 250 ° C. Outside the reaction temperature range, the same phenomenon as when the catalyst is a metal compound or a solid acid catalyst occurs, which is not preferable. As described in the Examples below, when the (hetero) polyacid is H ₃ PMo ₁₂ O ₄₀ .30H ₂ O, the desired product BH5HI is obtained at a reaction temperature of 190 ° C. in high yield, also, if a _{H 3 PW 1 2 O 40 ·} 6H 2 O is
BH5HI is obtained in high yield at a relatively low reaction temperature of 115 ° C.

In the present reaction, in order to make the reaction proceed, it is important to distill off generated water or alcohol.
In order to facilitate the distillation of water or alcohol, the pressure is preferably lower than normal pressure, more preferably lower pressure, than under pressure. This is because by performing the reaction under reduced pressure, the reaction temperature can be lower than that under normal pressure under the same reaction rate of esterification, and the reaction rate can be higher than under normal pressure at the same reaction temperature. . Practically, in order to raise the reaction temperature to more than 200 ° C., the cost of the apparatus, the heating medium, the energy and the like increase remarkably. Therefore, it is effective to reduce the reaction temperature to 180 ° C. or less by reducing the pressure during the reaction. .

The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

By tracking the reaction product by liquid chromatography, the reaction time can be set at the desired end point of the reaction. The reaction time varies depending on the molar ratio of the raw materials, the reaction temperature and the type of the catalyst used.

This reaction can be carried out in any of a batch reactor and a continuous reactor.

The bis (2-hydroxyethyl) 5-hydroxyisophthalate obtained in the present invention is useful as a polymer crosslinking agent.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. The analysis conditions for liquid chromatography are as follows. The area% of the target product BH5HI
Corresponded to the purity in the product organism (internal standard method). Model: Shimadzu LC-10A, Column: YMC-Pack
ODS-AM, column size: 4.6 x 250 mm I.
D. , Column temperature: 40 ° C, detection wavelength: UV220m
m, flow rate: 0.5 ml / min, eluent: H ₂ O / CH ₃
CN = 1/2

Example 1 9.1 g of 5-hydroxyisophthalic acid (5HI) (0.
05 mol), 124 g of ethylene glycol (2 mo
l) and 0.11 g of zinc acetate dihydrate (0.05 × 10
^-2 mol) (0.01 mol times of 5HI) with water separation tube 20
A 0 mL four-necked reaction flask was charged. The bath temperature was raised to 200 ° C. while stirring. From around 150 ° C. of the reaction solution temperature, the generated water started to distill into the water separation tube. The temperature of the reaction solution was raised to around 190 ° C. together with the distillation of water and part of ethylene glycol. When the temperature of the reaction solution was maintained for 2 hours, the distillation almost stopped. The heating and stirring were continued for another 4 hours to complete the reaction.
Subsequently, after cooling to 95 ° C., residual ethylene glycol was distilled off under reduced pressure. 40 g of acetone was added to and dissolved in the obtained highly viscous residue, and 0.27 g of activated carbon was further added, followed by refluxing for 2 hours. After cooling to 30 ° C., the activated carbon was removed by filtration, and then acetone was replaced with ethyl acetate under reduced pressure. After further cooling with ice, filtration and drying of the obtained solid under reduced pressure gave 11.2 g of white crystals. (81% yield)
The analysis results of this crystal were as follows.

MASS (FAB +, m / e (%)): 271 (M + 1, 47), 253 (3
7), 209 (100), 165 (100) 1 H-NMR (d 6 -DMSO, ppm): 3.72 (s, 4H), 4.31 (s, 4H), 4.98 (br,
2H), 7.63 (s, 2H), 8.01 (s, 1H), 11.6 (br, 1H) mp 148 ℃

Examples 2 to 22, Comparative Example 1 3.64 g of 5-hydroxyisophthalic acid (20 mmol)
Except that l) was charged in a 50 mL four-neck reaction flask equipped with a water separation tube, the reaction was conducted under the conditions shown in Table 1 and analyzed by liquid chromatography (LC). The results are shown in Table 1.

TABLE 1 Real HOCH ₂ CH ₂ OH catalytic reaction ───────────── ────── BH5HI Example g (molar ratio) ¹ type mg (mol%) ² Temperature Time LC area% No. ℃ h ────── ───────────────────────────── 2 25 (20) Zn ( OAc) 2 · 2H 2 O 44 (1) 190 2.5 39.3 3 25 (20) Zn (OAc ) 2 · 2H 2 O 220 (5) 190 3.5 89.5 4 25 (20) Zn (OAc) 2 · 2H 2 O 44 (1) 190 4 90.4 5 50 (40) Zn (OAc _{) 2 · 2H 2 O 44 (} 1) 190 2 95.6 6 25 (20) Zn (OAc) 2 · 2H 2 O 44 (1) 200 4 95.9 7 50 (40) Zn (OAc) 2 · 2H 2 O 9 ( 0.2) 195 4 80.1 8 6 ( 5) Zn (OAc) 2 · 2H 2 O 44 (1) 190 4 50.2 9 50 (40) Zn 13 (1) 190 8 93.2 10 50 (40) ZnSO 4 · 7H 2 O 58 (1) 190 4 91.4 11 50 (40) Zn (CH 2 COCH 2 COCH 3) 2 26 (1) 190 4 80.1 12 50 (40) Mn (OAc) 2 · 4H 2 O 49 (1) 190 5 93.2 13 50 (40) CuCl ₂ 27 (1) 150 2 23.7 14 50 (40) Cd (CH ₃ CO ₂ ) ₂・ 2H ₂ O 53 (1) 190 6 86.6 15 50 (40) 5 (NH ₄ ) ₂ O ・ 12WO ₃・ 5H ₂ O 364 (10wt%) ³ 190 6 85.2 16 50 (40) H ₂ WO ₄ 364 (10wt%) ³ 190 6 94.4 17 50 (40) 5 % Pd / C 426 (1) 190 7 37.6 18 50 (40) 5% Pd / Al ₂ O ₃ 426 (1) 190 7 36.5 19 50 (40) H ₃ PW ₁₂ O ₄₀・ 6H ₂ O 364 (10wt% ) ³ 115 5 85.7 20 50 (40) H ₃ PMo ₁₂ O ₄₀・ 30H ₂ O 364 (10wt%) ³ 190 2 48.0 21 25 (20) CH ₃ C ₆ H ₄ SO ₃ H ・ H ₂ O 38 (1 ) 110 7 91.8 22 25 (20) CH ₃ C ₆ H ₄ SO ₃ H ・ H ₂ O 190 (5) 110 2.5 88.1 Comparative Example 1 50 (40) None 190 2 18.8 ────────── ────────────────────────── ¹ mole ratio = (mol number of EG) / (mol number of 5HI) ² mol% = [(catalyst Moles) / (5HI moles)] × 100 ³ wt% =% by weight based on the weight of 5HI

Examples 23-33 5.0 g (27.5 mmol) of 5-hydroxyisophthalic acid
l) and 68.2 g of ethylene glycol (40 times the molar amount of 5HI) were charged and reacted in a 100 mL four-necked flask equipped with a water separation tube, and the results of the reaction were summarized in the same table.

Table 2 ─────────────────────────────── Actual catalyst reaction application H ─────── BH5HI Example Type mg (mol%) ² Temperature Time LC area% No. ℃ h ────────────────── ───────────── 23 ZnCl ₂ 40 (1) 150 5 45.7 24 AlCl ₃ 30 (1) 195 2 34.8 25 FeCl ₃ 50 (1) 195 5 70.4 26 Yb (CF ₃ SO ₃ ) ₃ 170 (1) 150 5 78.0 27 TiO (CH ₂ COCH ₂ COCH ₃ ) ₂ 170 (1) 195 5 88.6 28 K-10 50 (1wt%) ³ 195 5 43.7 29 * 1 98% H ₂ SO ₄ 50 (1.8) 100 8 72.8 30 * 2 98% H ₂ SO ₄ 50 (1.8) 100 8 87.7 31 35% HCl 200 (10) 110 5 85.4 32 35% HCl 400 (20) 80 9 81.6 33 Amberlyst 15 50 (1wt %) ³ 120 16 72.5 ─────────────────────────────── * 1: 17 g of EG (10 times mol of 5HI) use * 2:. EG a 85g used (50-fold molar 5HI) ^2:. mol% = (number of moles of catalyst) / (number of moles of 5HI) × 100 ^3: w t% = weight% based on the weight of 5HI

Example 34 5 g of 5-hydroxyisophthalic acid (27.5 mmol
l), ethylene glycol 250 g (147 times mol of 5HI) and zinc acetate dihydrate 0.06 g (1 mol)
%) Was charged into a 500 mL four-necked reaction flask equipped with a water separation tube, and reacted at 175 ° C. for 4 hours under a reduced pressure of 40 kPa. Liquid chromatography (LC) of the reaction solution
As a result of the analysis, the target BH5HI was produced at 93.9 area%.

Example 35 50 g of 5-hydroxyisophthalic acid (0.275 mol
l), 853 g of ethylene glycol (50 times the mole of 5HI) and 0.5 g (1 wt%) of 98% H ₂ SO ₄ were charged into a 1 L four-necked reaction flask equipped with a water separation tube, and the reaction solution temperature was 100 ° C. under reduced pressure of 4 kPa. For 20 hours. As a result of analyzing the reaction solution by liquid chromatography (LC), the target BH5HI was found to be formed at 93.2 area%.

Example 36 4.2 g of dimethyl 5-hydroxyisophthalate (0.0 g)
2 mol), ethylene glycol 150 g (0.8 mol) and manganese acetate tetrahydrate 0.05 g (1 mol)
%) Was charged into a 100 mL four-necked reaction flask equipped with a water separation tube. The bath temperature was raised to 200 ° C. while stirring. From around 150 ° C. of the reaction solution temperature, the produced methanol began to distill into the water separation tube. The temperature of the reaction solution was raised to around 190 ° C. together with the distillation of methanol and part of ethylene glycol. When the temperature of the reaction solution was maintained for 1 hour, the distillation almost stopped. The heating and stirring were continued for an additional hour to complete the reaction. Subsequently, after cooling to 95 ° C., residual ethylene glycol was distilled off. 40 g of acetone was added to the obtained highly viscous pot residue and dissolved, and then 0.27 g of activated carbon was further added, and the mixture was heated for 2 hours. Reflux. 30 ° C
After cooling to room temperature, the activated carbon was removed by filtration, and then acetone was replaced with ethyl acetate under reduced pressure. After further cooling with ice, filtration and drying of the obtained solid under reduced pressure gave white crystals 4.48.
g was obtained (83% yield). This crystal is MASS, ¹ H
From the analysis results of NMR and melting point, bis (2-hydroxyethyl) -5-hydroxyisophthalate (BH5H
I) was confirmed.

Examples 37 to 45, Comparative Example 2 Liquid chromatography (LC) was carried out in the same manner as in Example 36 except that the molar ratio of ethylene glycol, the type and mole% of the catalyst, the temperature and the time were changed. Table 3 summarizes the results of the analysis in (3). Table 3 ──────────────────────────────────── Real HOCH ₂ CH ₂ OH catalyst reaction ─ H ──────── BH5HI Example g (molar ratio) ¹ type mg (mol%) ² Temperature Time LC area% No. ℃ h ─────── ───────────────────────────── 37 25 (20) H ₂ WO ₄ 50 (1) 190 2 42.6 38 50 (40) _{H 2 WO 4 100 (2)} 190 3 77.9 39 50 (20) H 2 WO 4 100 (2) 197 4 97.3 40 25 (20) Zn (OAc) 2 · 2H 2 O 9 (0.2) 190 3 92.5 41 50 _{(40) Zn (OAc) 2} · 2H 2 O 18 (0.4) 190 2 96.3 42 50 (40) Zn (OAc) 2 · 2H 2 O 220 (5) 170 3 92.6 43 25 (20) Zn (OAc) 2・ 2H ₂ O 190 (5) 120 4 73.7 44 25 (20) CH ₃ C ₆ H ₄ SO ₃ H ・ H ₂ O 100 (5) 110 15 69.8 45 25 (20) 97% H ₂ SO ₄ 110 8 71.3 Comparative Example 2 50 (40) None 190 3 23.6 ──────────────────────────────────── ¹ molar ratio = (Number of moles of EG) / (5-hydroxyi Phthalic acid number of moles of dimethyl) ² mol% = [(moles of catalyst) / (number of moles of 5-hydroxy-isophthalic acid dimethyl)] × 100

[0039]

According to the present invention, (1) 5-hydroxyisophthalic acid and (2) 5 in the presence of metals and metal compounds of Groups 1 to 8 of the periodic table as catalysts, mineral acids, organic acids and solid acids.
-5 to each of the dialkyl hydroxyisophthalates
By reacting 200 times moles of ethylene glycol, (1) is subjected to esterification by condensation dehydration and (2) is esterified by transesterification to easily obtain bisphenol with high purity and high yield. (2-Hydroxyethyl) 5-hydroxyisophthalate (BH5
HI) can be obtained.

Continued on the front page (72) Inventor Yoko Ohkuni 722-1 Tsuboi-cho, Funabashi-shi, Chiba F-term in Nissan Chemical Industry Co., Ltd. Central Research Laboratory 4H006 AA02 AC48 BA07 BA08 BA09 BA10 BA13 BA14 BA19 BA30 BA32 BA34 BA35 BA36 BA37 BA66 BA68 BA75 BC10 BJ50 BN10 BN30 KA03 KA30 4H039 CA66 CE10

Claims (12)

[Claims] (1) Formula (1) (Wherein, R represents a hydrogen atom or an alkyl group.) A bis (2-hydroxyethyl) 5-hydroxyisophthalate is obtained by heat-treating a 5-hydroxyisophthalic acid compound represented by the following formula and ethylene glycol in the presence of a catalyst. A process for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate, wherein ethylene glycol is used in an amount of 5- to 200-fold the molar amount of the 5-hydroxyisophthalic acid compound. 2. The bis (2) catalyst according to claim 1, wherein a metal of Group 1 to Group 8 of the periodic table and a metal compound thereof or a solid acid are used as the catalyst, and the reaction temperature is 130 to 250 ° C.
-Hydroxyethyl) 5-hydroxyisophthalate production process. 3. The metal of Group 1 to Group 8 of the periodic table and the metal of a metal compound thereof are selected from the group consisting of zinc, tungsten, manganese, titanium, cadmium, iron, antimony, aluminum, scandium and lanthanide-based rare earths. The method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 2, which is at least one selected metal. 4. The metal of Group 1 to Group 8 of the periodic table and the metal compound thereof used in the catalyst are at least one selected from zinc, tungsten, manganese, titanium, iron, ytterbium and palladium. The method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 3, which is a metal of the formula (1). 5. The metal of Group 1 to Group 8 of the periodic table and their metal compounds used for the catalyst are zinc, tungsten, manganese, Pd / activated carbon, Pd / alumina, Zn
(CH ₃ CO ₂ ) ₂ , ZnSO ₄ , Mn (CH ₃ CO ₂ ) ₂ ,
WO ₃ , H ₂ WO ₄ , 5 (NH ₄ ) ₂ · 12WO ₃ , TiO
(CH ₂ COCH ₂ COCH ₃ ) ₂ , FeCl ₃ , Yb (C
F ₃ SO ₃₎ bis (2-hydroxyethyl) 5-hydroxy isophthalate method according to claim 4 is at least one metal or metal compound selected from among _3. 6. The bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 2, wherein the solid acid used for the catalyst is at least one solid acid selected from silica, alumina, silica alumina and zeolite. Manufacturing method. 7. The method according to claim 1, wherein a proton acid or a cation exchange resin is used as a catalyst, and the reaction temperature is 80 to 150 ° C.
3. The method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to 1.). 8. The method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 7, wherein the protonic acid used for the catalyst is a mineral acid, an aliphatic carboxylic acid or a sulfonic acid. 9. The process for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 7, wherein the protonic acid used for the catalyst is sulfuric acid, hydrochloric acid or p-toluenesulfonic acid. 10. A (hetero) polyacid as a catalyst,
The method for producing bis (2-hydroxyethyl) 5-hydroxyisophthalate according to claim 1, wherein the reaction temperature is 80 to 250 ° C. 11. The (hetero) polyacid used for the catalyst is H
_ThreePW₁₂O₄₀, H₆P _TwoW₁₈O₆₂, H₇PW₁₁O₃₉, H₇P
(W_TwoO₇)₆, H_FourSiW₁₂O₄₀, H_FourTiW₁₂O₄₀, H_Five
CoW₁₂O₄₀, H_FiveFeW₁₂O₄₀, H_0.5Cs_2.5PW₁₂
O₄₀, H_TwoMoO_Five, H_ThreePMo₁₂O₄₀, H₆P_TwoMo₁₈O
₆₂, H₇PMo₁₁O₃₉, H_ThreePMo₆W₆O ₄₀And H_FourPM
oW₁₁O₄₀At least one (hetero) selected from
The bis (2-hydroxy) according to claim 10, which is a polyacid.
Ethyl) method for producing 5-hydroxyisophthalate. 12. The (hetero) polyacid used for the catalyst is H
₃ PW ₁₂ O ₄₀ and H ₄ PMoW ₁₁ bis (2-hydroxyethyl) 5-hydroxy isophthalate method according to claim 10 which is selected at least one (hetero) polyacid among O _40.