JPH0627085B2 - Process for producing hydrogenated bisphenols - Google Patents

Description

The present invention relates to an improvement in a method of hydrogenating bisphenols under pressure in the presence or absence of a solvent using Raney-Nitzel as a catalyst.

Hydrogenated bisphenols, which are hydrogenated products of bisphenols, are a kind of alicyclic diols and are important materials as a characteristic resin component or resin modifying component. For example, hydrogenated bisphenol A obtained by hydrogenating bisphenol A (4,4′-dihydroxydiphenyl-2,2-propane) is a hydrogenated bisphenol A which is treated with a dibasic acid such as phthalic acid, maleic acid or adipic acid. When it is polycondensed, it becomes a polyester resin having heat resistance and moisture resistance, which has been praised as a material for daily necessities and a material for industrial goods. When hydrogenated bisphenol A is reacted with epichlorohydrin, a low-viscosity epoxy resin having excellent electrical characteristics can be obtained. Furthermore, bisphenol F (2,2 '
As for hydrogenated bisphenol F obtained by hydrogenating-, 2,4'- and 4,4'-dihydroxydiphenylmethane isomer mixture), its use is largely for future research. , And is expected to have applications similar to those of hydrogenated bisphenol A.

By the way, looking at the publicly known documents relating to the method for producing hydrogenated bisphenol A, first, Chieco Slovak Patent No.
No. 72, 10 wt% relative to bisphenol A
It is described that hydrogenation of bisphenol A is carried out for 8 hours under the conditions of 200 ° C. and 40 kg / cm ² by using Raney-Nickel as described above and using methylcyclohexanol as a solvent.
Further, in Japanese Examined Patent Publication No. 42-1423, hydrogenation of bisphenol A is carried out for 4 hours under the condition of using 6 wt% of Raney-Nickel to bisphenol A and using n-butanol as a solvent at 200 ° C. and 80 kg / cm ^2. An example is shown. On the other hand, an example of hydrogenating bisphenol F is Japanese Patent Publication No. 50-10.
See No. 636, in which 5 wt% of Raney-Nickel to 4,4'-dihydroxydiphenylmethane is used, and methanol is used as a solvent at 180 ° C. and 100 kg / cm ^2.
Hydrogenation is carried out for 3 hours under the conditions.

Thus, according to the prior art, in order to perform hydrogenation at a relatively low pressure, a large amount of Raney-Nickel must be used. There was the inconvenience of having to use hydrogen.

The present inventors, when hydrogenating bisphenols, the amount of Raney-Nitzkel used is 1.5 to bisphenols.
Keep it as small as 3wt% and relatively low pressure, ie 40 ~
As a result of continued intensive research on means for hydrogenating at 60 kg / cm ² , hydrogenation was carried out by allowing a small amount of alkaline earth metal hydroxide, especially calcium hydroxide or magnesium hydroxide to coexist in the reaction system. The present inventors have completed the present invention by finding that the rate is remarkably accelerated and the desired hydrogenation can be carried out. The effect of accelerating the reaction by the alkaline earth metal hydroxide has not been found in the conventional literature, and the present invention has the industrial value in that it can save the amount of the catalyst used and shorten the hydrogenation reaction time. Is extremely large.

Thus, the method for producing hydrogenated bisphenols according to the present invention, when hydrogenating the bisphenols in the presence or absence of a solvent using Raney-Nitzkel as a catalyst, a small amount of alkaline earth metal water is added to the reaction system. The feature is that an oxide coexists.

In the present invention, the bisphenols used as raw materials include the above-mentioned bisphenol A and bisphenol F,
4,4'-dihydroxydiphenylmethylethylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2-propane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, etc. Various homologues can be used and any of them can be hydrogenated in the present invention. The hydrogenation of the present invention can be carried out without a solvent, but a solvent can be used if necessary,
Suitable solvents are lower alcohols such as methanol, ethanol, isopropanol and butanol. Of these, isopropanol is preferable. The amount of the solvent 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 smaller than that in the conventional method and is in the range of 0.5 to 5 wt%, preferably 1.5 to 3 wt% of the raw material bisphenols. And in the present invention, 10 to 100 wt% of the Raney-Nitzkel catalyst, preferably 1
6 to 36 wt% of alkaline earth metal hydroxide is made to coexist in the reaction system in a powder state. The reaction temperature is 120-
A temperature of 220 ° C., preferably 180 to 190 ° C. is adopted, and a hydrogen pressure of 40 to 60 kg / cm ² is generally adopted.
The amount of the Raney-Nickel catalyst used is not necessarily limited to the above range, and when the reaction time is to be further shortened, a larger amount of the Raney-Nickel catalyst can be used.

When carrying out the method of the present invention, first, the raw material bisphenols are supplied to an autoclave together with an appropriate amount of a solvent if necessary, and a predetermined amount of the Raney-Nitzkel catalyst and an alkaline earth metal hydroxide are added thereto. Next, after replacing the air in the autoclave with hydrogen, start heating with stirring,
Reaction temperature 120-220 ° C, preferably 180-190
Hydrogenation of bisphenols is generally carried out under the conditions of ° C and hydrogen pressure of 60 kg / cm ² . In this case, since the hydrogen pressure decreases as the reaction progresses, for example, when the pressure is reduced to 40 kg / cm ² , the operation of pressurizing again to 60 kg / cm ² is repeated, and hydrogen is absorbed until the hydrogen pressure no longer decreases. Here, heating is stopped and the autoclave is cooled. In the case of using no solvent, the solvent is added to the reaction mixture and the catalyst and the alkaline earth metal hydroxide are separated by filtration. Next, the filtrate is distilled under reduced pressure to distill off the solvent until the hydrogenated bisphenols start to distill out slightly, whereby the desired product, hydrogenated bisphenols, can be obtained in the form of a distillation residue. The hydrogenated bisphenols thus obtained can be further distilled for purification if necessary. In any case, hydrogenated bisphenols are obtained as a colorless transparent solid.

Hereinafter, the present invention will be described more specifically with reference to Examples, but these Examples do not limit the present invention.

Example 1 110 g of bisphenol A and 1 of isopropanol were added to a 500 cc electromagnetic vertical stirring autoclave made of SUS 304.
65 g, Raney-Nitzkel 4.6 g (N1 manufactured by JGC Chemicals Co., Ltd.)
52D = developed product) and 0.55 g of calcium hydroxide (16.
(7 wt% to Raney-Nickel), the air in the autoclave was replaced with hydrogen, and heated at 130 rpm while stirring to increase the hydrogen pressure to 60 kg / cm ² while maintaining the reaction temperature of 185 to 190 ° C. This is a place having conducted the reaction by repeating the operation to boost the 60 kg / cm ² again Tara under month 40 kg / cm ^2, hydrogen absorption was completed in 7 hours. Then, the autoclave was cooled, and the content was filtered to separate the catalyst and calcium hydroxide. The obtained filtrate was vaporized to a point where hydrogenated bisphenol A started to be slightly distilled, that is, to a distillation vapor temperature of 165 ° C./7 mmHg to recover isopropanol and the distillation residue was used as a product.

The obtained hydrogenated bisphenol A was colorless and transparent,
The yield was 115.3 g, the yield was 99.6% (vs. theoretical value q), and the OH number was 445.

Comparative Example 1 When the reaction was carried out under the same conditions as in Example 1 except that calcium hydroxide was not added, it took 25 hours to complete the hydrogen absorption. Product yield 111g, reduced yield 95.6%
(Vs theoretical value), OH number was 435.

The time required for hydrogen absorption was 7 hours in Example 1, whereas it was 25 hours in Comparative Example 1, as is apparent from the fact that the addition of calcium hydroxide significantly reduces the reaction time. I understand.

Example 2 The reaction was performed in exactly the same manner as in Example 1 except that the amount of calcium hydroxide added was 1.1 g (33.3 wt% relative to Raney-Nickel), and no isopropanol was used.
Hydrogen absorption was completed in 11 hours. Product yield is 111g,
The OH number was 449.2.

Example 3 Bisphenol F was added to the autoclave used in Example 1.
(4,4'-body 33.18%, 2,4'-body 44.06%,
2,2'-body 12.75%, novolak body 9.96%) 25
0 g, Raney-Nickel (N152D) 5.2 g and calcium hydroxide 1.25 g (33.3 wt% to Raney-Nickel) were charged, and after replacing the air in the autoclave with hydrogen, 13
The liquid temperature is 170-185 by heating with stirring at 0 rpm.
℃ hydrogen pressure was raised to 60 kg / cm ² while maintaining, at which having conducted the reaction by repeating the operation to boost the 60 kg / cm ² again Once dropped to 40 kg / cm ^2, hydrogen uptake is 6 hours 3
It finished in 0 minutes. The reaction product was once cooled, 250 g of isopropanol was added and dissolved, and the catalyst and calcium hydroxide were separated by filtration at room temperature. Next, until the hydrogenated bisphenol F is partially distilled from the filtrate, that is, the distillation temperature is 153 ° C.
Distilled up to about / 7 mmHg to recover isopropanol, and use the distillation residue as a product.

The obtained hydrogenated bisphenol F was a colorless transparent solid at room temperature, and the yield was 251.5 g, the yield was 94.9% (relative to the theoretical value), and the OH value was 510.

Example 4 100 g of bisphenol F, 150 g of isopropanol, Raney-Nitzkel (N152D) 2.1 in an autoclave
g and magnesium hydroxide 0.5 g (33.3 wt% to Raney-Nickel) were charged in exactly the same manner as in Example 3, but hydrogen absorption was completed in 5 hours and 10 minutes.
The reaction product was treated in the same manner as in the previous example to obtain hydrogenated bisphenol F which was a colorless transparent solid at room temperature. Yield 10
0.7 g, yield 95% (vs theoretical), OH number 507.

Comparative Example 2 Except that magnesium hydroxide was not used, the reaction was carried out under the same conditions as in Example 4 to obtain hydrogenated bisphenol F having substantially the same yield and substantially the same yield as in Example 4. But,
In this example, it took a long time of 20 hours to complete the absorption of hydrogen.

Claims (4)

[Claims] 1. A small amount of an alkaline earth metal hydroxide is allowed to coexist in the reaction system when pressurized hydrogenation of bisphenols is carried out in the presence or absence of a solvent using Raney-Nitzkel as a catalyst. Method for producing hydrogenated bisphenols. 2. The amount of the alkaline earth metal hydroxide is
A method according to claim 1 which is 10 to 100 wt% of the Raney-Neckel. 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.