JPS61260034A - Production of hydrogenated bisphenol compound - Google Patents

Abstract

PURPOSE:To produce the titled compound saving the amount of catalyst and shortening the hydrogenation reaction time, by the hydrogenation of a bisphenol compound under pressure in the presence of a Raney-nickel catalyst using a small amount of a specific compound as a reaction accelerator, if necessary in a solvent. CONSTITUTION:The objective compound is produced as a colorless transparent solid by hydrogenating a bisphenol compound such as bisphenol A under the hydrogen pressure of 40-60kg/cm<2> at 120-220 deg.C in the presence of a Raney- nickel catalyst, preferably in a solvent such as isopropanol or in the absence of a solvent, using a small amount of an alkaline earth metal hydroxide, especially Ca(OH)2, Mg(OH)2, etc., as a reaction accelerator. The amount of the Raney-nickel catalyst is 0.5-5wt%, preferably 1.5-3wt% of the bisphenol compound used as the raw material. The alkaline earth metal hydroxide is used in powdery state in an amount of 10-100wt%, preferably 16-36wt% based on the Raney-nickel catalyst. USE:A resin component, a resin modifier component, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for pressurized hydrogenation of bisphenols using Raney nickel as a catalyst in the presence or absence of a solvent.

Hydrogenated bisphenols, which are hydrogenated products of bisphenols, are a type of alicyclic diol and are important materials as characteristic resin components or resin modifying components. For example, hydrogenated bisphenols obtained by t-hydrogenation of bisphenol A (4,4'-dihydroxydiphenyl-2,2-pronocene) are polycondensed with dibasic acids such as phthalic acid, maleic acid, and adipic acid. The result is a heat-resistant and moisture-resistant polyester resin, which is prized as a material for daily necessities and industrial goods. When hydrogenated bisphenols are reacted with epichlorohydrin, a low-viscosity epoxy resin with excellent electrical customization properties can be obtained. Furthermore, bisphenol F
Regarding hydrogenated bisphenol F obtained by t-hydrogenation (isomeric mixture of 2°g, 2.4!- and 4.4'-dihydroxydiphenylmethane), □ Its uses are subject to future research. Although large, it is expected to have uses similar to hydrogenated bisphenols.

By the way, when we look at publicly known documents regarding the production method of hydrogenated bisphenols, we first find Czechoslovakia Patent No. 103.
Specification No. 572 states that 10w against bisphenols
It is described that hydrogenation of bisphenols using t% Raney nickel and methyl cyclohexanol as a solvent at 200° C. and 40 kg/am” for 8 hours.

Furthermore, in Japanese Patent Publication No. 1423/1983, 6 wt% Raney nickel is used for bisphenol A IC, and n-
An example is shown in which bisphenol Ai is hydrogenated for 4 hours at 200°C and 80°C using butanol as a solvent. - An example of hydrogenating bisphenol F can be found in Japanese Patent Publication No. 10636/1983, in which 4
, 5 w for 4'-dihydroxydiphenylmethane
Using t% Raney nickel and methanol as a solvent, hydrogenation was carried out at 180°C and 100ky/am''.
Been done for hours.

Thus, according to the prior art, in order to perform hydrogenation at relatively low pressure, a large amount of Raney nickel must be used, and if Raney nickel is saved and its usage is reduced, it is possible to perform hydrogenation at relatively high pressure. There was an inconvenience that hydrogen had to be used.

The present inventors have determined that when hydrogenating bisphenols, the amount of Raney nickel used is 1.5 per bisphenol.
As a result of intensive research into methods for hydrogenation in small amounts of ~3 wt% and at relatively low pressures, i.e., 40 to 60 kg/cm2, we found that hydrogenation of small amounts of alkaline earth metal hydroxides, especially calcium hydroxide Alternatively, they have discovered that by coexisting magnesium hydroxide in the reaction system, the hydrogenation rate can be significantly accelerated, and the desired hydrogenation can be carried out.
The invention has been completed. The effect of accelerating the reaction by alkaline earth metal hydroxides has not been found in conventional literature, and the present invention has an industrial advantage in that it enables saving of catalyst waste and shortening the hydrogenation reaction time. The value is extremely large.

Therefore, in the method for producing hydrogenated bisphenols according to the present invention, when bisphenols are hydrogenated in the presence or absence of a solvent as a Raney nickel catalyst, a small amount of alkaline earth metal hydroxide is added to the reaction system. It is characterized by the coexistence of

In the present invention, the bisphenols used as raw materials include the above-mentioned bisphenols and bisphenol F.
Various congeners such as 4,4'-dihydroxydiphenylmethylethylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2-propane%'#4'-dihydroxydiphenyl-1,1-cyclohexane, etc. Any of these can be hydrogenated in the present invention. Although the hydrogenation of the present invention can be carried out without a solvent, a solvent can also be used if necessary, and lower alcohols such as methanol, ethanol, isopropanol, butanol are suitable as the solvent. Among them, Improper Tools are preferred. The amount of solvent to be used is usually selected in the range of 1 to 2 times the weight of the raw material bisphenols.

The amount of Raney nickel used in the present invention is small compared to conventional methods, and is 0.5 to s wt of the raw material bisphenols.
H, preferably in the range of 1.5 to 3 wt%. In the present invention, 10 to 100 wt% of the Raney nickel catalyst
, preferably 16 to 36 wt., of alkaline earth metal hydroxide is allowed to coexist in the reaction system in powder form. The reaction temperature is 120 to 220°C, preferably 18ON190
'C is adopted, and the hydrogen pressure is 40 to 60 kp/"c
m'' is generally adopted.The amount of Raney nickel catalyst used is not necessarily limited to the above range, and if the reaction time is to be shortened to 1. can be used.

When carrying out the method of the present invention, raw material bisphenols are first supplied to an autoclave together with an appropriate amount of solvent as required, and predetermined amounts of Raney nickel catalyst and alkaline earth metal hydroxide are added thereto. Next, after replacing the air in the autoclave with hydrogen, heating was started with stirring.
Reaction temperature: 120-220°C, preferably 180-19
It is common to hydrogenate bisphenols under the conditions of 0°C and hydrogen pressure of 60 ky/cm. In this case,
As the reaction progresses, the hydrogen pressure decreases, so for example 40
When the pressure drops to 60 kt/cm"
``Repeat the pressurization operation to absorb hydrogen until the hydrogen pressure no longer decreases.

At this point, the heating is stopped and the autoclave is cooled. If no solvent is used, a solvent is added to the reaction mixture and the catalyst and alkaline earth metal hydroxide are filtered off. Next, the filtrate is distilled under reduced pressure to remove the solvent until a slight amount of hydrogenated bisphenols begins to distill out, thereby obtaining the desired product, hydrogenated bisphenols, in the form of a distillation residue. The hydrogenated bisphenols thus obtained can be further purified by distillation, if necessary. In any case, the hydrogenated bisphenols are obtained as a colorless and transparent solid.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but these Examples are not intended to limit the present invention.

Example 1 In a 500eC electromagnetic vertical stirring autoclave made of 8U8304, 110 g of bisphenol A and 1 isopropanol were added.
65 g, Raney nickel 4.6 g (8 Kiku Kagaku Co., Ltd.)
manufactured by N152D = developed product) and calcium hydroxide 0.55
g (16.7 wt% vs. Raney nickel), and after replacing the air in the autoclave with hydrogen, 130 r, 9
．． While maintaining the reaction temperature of 185 to 190"C, increase the hydrogen pressure to t-60#/Cm", and when this drops to 40 kP/cm", increase the hydrogen pressure to 60 kP/cm" again.
When the reaction was carried out by repeating the operation of increasing the pressure to "t/cm", hydrogen absorption was completed in 7 hours. After that, the autoclave was cooled and the contents were filtered by tM to separate the catalyst and calcium hydroxide. The point at which hydrogenated filtrate begins to be slightly distilled, that is, the distillate vapor temperature is 165
The mixture was distilled at 77 mmHg to recover isopropropylene and R-nor, and the distillation residue was used as a product.

The obtained hydrogenated bisphenol A is colorless and transparent,
Yield: 115.3g, Yield: 99.6cm (vs. theoretical value), OH
The value was 445.

Comparative Example 1 Implementation fI11 except that calcium hydroxide was not added
When the reaction was carried out under exactly the same conditions as above, it took 25 hours to complete hydrogen absorption. Product yield: 111g, yield: 95.
6% (relative to theoretical value), OH value 435.

The time required for hydrogen absorption was 7 hours in Example 1, while it was 25 hours in Comparative Example 1, which shows that the addition of calcium hydroxide significantly shortens the reaction time. .

Example 2 The amount of calcium hydroxide added was 1.1 g (33.3w
t s vs. Raney nickel) and the reaction was carried out in exactly the same manner as in Example 1 except that impropatol was not used, and hydrogen absorption was completed in 11 hours. The product yield was 111 g, and the OH value was 449.2.

Example 3 Bisphere/I was added to the autoclave used in Example 1.
/F (4,4' integral 33.18%, 2.4' integral 44
．． 06%, 2,2′ integrated 12.75%, nolac body 9
．． 96%) 250g, Raney Nickel (N 152D)
5.2 g and calcium hydroxide 1.25 g (33,
After replacing the air in the autoclave with hydrogen, heat the autoclave with stirring at 130 r, p, m to maintain the liquid temperature at 170 to 185°C and raise the hydrogen pressure to f 60 kg/cm". Boost the voltage and this is 40k
When the pressure decreased to 60 kg/cm'', the reaction was repeated to increase the pressure to 60 kg/cm'', and the reaction was completed in 6 hours and 30 minutes with hydrogen absorption. The reaction product was once cooled, and 250 g of isopropropylene and e-Nol were added and dissolved, and then the catalyst and calcium hydroxide were filtered off at room temperature.

Next, the filtrate was distilled until a portion of hydrogenated bisphenol F began to be distilled out, that is, until the distillation temperature reached about 153"C/7 mmHg, to recover isopro/9-nol, and the distillation residue was used as a product.

The obtained hydrogenated bisphenol F was a colorless and transparent solid at room temperature, with a yield of 251.5 g, a yield of 94.9% (based on theory), and a 00 value of 510.

Example 4 100g of bisphenol F in the autoclave.

Isoproper tool 150g, Raney nickel (N152
D) 2.1 g and magnesium hydroxide 0.5 g (33,
Example 3 except that 3 wt% of Raney nickel) was charged.
When the reaction was carried out in exactly the same manner as above, hydrogen absorption took place for 5 hours.
Finished in 0 minutes. The reaction product was treated in the same manner as in the previous example to obtain hydrogenated bisphenol F, which is a colorless and transparent solid at room temperature.
t- got it.

Charge xOO, 7g, yield 95% (vs. theoretical value), OH value 5
07° Comparative Example 2 A reaction was carried out under exactly the same conditions as in Example 4, except that magnesium hydroxide was not used, and hydrogenated bisphenol F having almost the same yield and quality as in Example 4 was obtained. but,
In this example, it took as long as 20 hours to complete hydrogen absorption.

Claims (1)

[Claims] 1. When performing pressurized hydrogenation of bisphenols using Raney nickel as a catalyst in the presence or absence of a solvent, a small amount of alkaline earth metal hydroxide is allowed to coexist in the reaction system. A method for producing hydrogenated bisphenols. 2. Claim 1, wherein the amount of the alkaline earth metal hydroxide is 10 to 100 wt% of Raney nickel.
The method described in section. 3. The method according to claim 1, wherein the alkaline earth metal hydroxide is calcium hydroxide. 4. The method according to claim 1, wherein the alkaline earth metal hydroxide is magnesium hydroxide.