JPS60228438A - Production of monoalkylphenol - Google Patents

Abstract

PURPOSE:In the production of the titled compound by reaction of phenol with an olefin, a strong-acid styrene-sulfonic acid type cation exchange resin is used as a catalyst to increase the conversion of olefine and improve the yield with reduced formation of by-products. CONSTITUTION:A polystyrene-solfonic acid type cation exchange resin of high thermal stability and increased acidity is used as a catalyst to effect the reaction of phenol with a 12-30C olefin, preferably 1mol of the olefin with 2-3mol of phenol, to give the objective compound. Dice ion EX-145H made by Mitsubishi Chemical Co. is cited as a catalyst cited above.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing monoalkylphenol in high yield by reacting phenol with an olefin.

Conventional methods for producing alkylphenols from phenol and olefins include aluminum chloride, sulfuric acid,
Methods using hydrogen chloride, boron trifluoride, etc. as catalysts are known.

However, all of these catalysts are corrosive, so
After the reaction, complicated post-treatments such as water washing or alkaline washing are required.

On the other hand, as a model that eliminates these drawbacks,
Publication No. 16781 discloses that acid clay or activated clay is used as a catalyst at °C, and phosphorus compounds such as phosphoric anhydride and its salts and phosphoric acid and its salts are allowed to coexist during the reaction, thereby significantly increasing the catalytic ability. It is disclosed that the catalyst enables the reaction to be carried out under milder conditions than when acid clay or activated clay is used alone.

However, these catalysts have the disadvantage that they are cheap, cannot be reused, and must be discarded once used.

In addition, in order to obtain alkylphenol in high yield,
As the molecular weight of the olefin used increases, the reaction temperature must be increased, resulting in the formation of polyalkylphenols, olefin decomposition and polymerization.

The present inventors have focused on using a special sulfonic acid type resin with increased acidity as a catalyst as a method for overcoming the above-mentioned drawbacks.

Although the special sulfonic acid type resin is much more expensive than the above-mentioned white earth and white earth/phosphoric acid type resins, it can be reused many times, and its lifespan depends on the type of resin. Even when used continuously, it can be used for one month.

Therefore, it is more economical than white earth and white earth/phosphoric acid systems.

Furthermore, for high molecular weight olefins having 1-2 or more carbon atoms, the reaction temperature is relatively low at about 100°C (130°C for white earths).
~170°C, 100-120°C for white earth/phosphoric acid)
Since it can act effectively and produce alkylphenol, it is possible to suppress the polymerization and decomposition of the raw material olefin, as well as by-products such as polyalkylphenols other than the target monoalkylphenol. Monoalkylphenol can be produced with high purity (high proportion of monoalkylphenol in the produced alkylphenol).

The ultimate objective of the present inventors is to increase the reaction rate of olefin when reacting phenol and olefin to produce alkylphenol, suppress the by-product of polyalkylphenol as much as possible, and suppress decomposition and polymerization of olefin. The object of the present invention is to provide the best catalyst for obtaining monoalkylphenol in high yield while taking reaction temperature and economic efficiency into consideration.

In the present invention, a strongly acidic polystyrene-based sulfonic acid type cationic resin with increased acidity (for example, Diaion EX-145H manufactured by Mitsubishi Kasei (Ha)) has a higher olefin reaction rate and monoalkylphenol yield than the above-mentioned white earth/phosphoric acid catalyst. This shows results that are several orders of magnitude better in terms of efficiency (based on olefins).

Table 1 In addition, in the present invention, the number of carbon atoms in the olefin is 12 to 30.
However, if the number of carbon atoms is 10 or less, Ambe
rlyst 15 (U.S. Om 77 Doha's Company) Revachit 5PC-108, Revatit 5pc-1
This is because it is less likely to obtain monoalkylphenol in a high yield than when a commonly used strongly acidic polystyrene-based sulfonic acid type cationic resin such as 18. (Bayer AG) is used as a catalyst.

In the present invention, a strongly acidic polystyrene-based sulfonate type cationic resin with increased acidity, such as Diaion EX-145H, has an acidity function value of -1 to -3;
The acidity is 1 point higher than general strong acidic polystyrene-based sulfonic acid type cationic resins (acidity function value is 2 to 3).

The above Diamondion EX-145H has 12 to 30 carbon atoms.
This effect is particularly expected for olefins (Table-
22 Table-3 and Table-4).

A further advantage of the present invention is that since the proportion of polyalkylphenol present in the reaction product is small, there is no need to separate monoalkylphenol and polyalkylphenol under high vacuum, resulting in considerable energy savings. It is possible.

In the alkylation of phenol, the use of a sulfonic acid resin as a catalyst is disclosed in Japanese Patent Publications No. 37-18182 and No. 40-21411, U.S. Patent No. 3,
639,490, Fang No. 4,168,390 and Fang 4
．． It is disclosed in the specification of No. 198,531 and the like. However, many of these target olefins having 12 or less carbon atoms, and none of them are capable of obtaining monoalkylphenol in high yield from phenol and olefins having 12 to 30 carbon atoms, as in the method of the present invention. Not listed.

The olefin in the present invention is a compound having a carbon-carbon double bond, and industrial examples include ethylene, propylene, butene, and alpha olefins.

Although the ratio of phenol and olefin used in the reaction can be varied depending on the purpose, the effective economic molar ratio for introducing an alkyl group into phenols is 2 to 3 moles of phenol to 1 mole of olefin. be.

Table-2 By Diaion EX-145H Table-3 by Amberlyst 15 Yield t is based on niolefin.

Next, the present invention will be explained by examples.

(Example 1) In a reaction vessel equipped with a stirrer, a thermometer, an inert gas inlet, and a heating and cooling device, 94.1 parts of phenol and a mixed olefin of hexadecene and octadecene (molecular weight 23) were added.
Add 115.5 parts and heat to 80° C. in a N2 atmosphere. Thereafter, 10 parts of Diaion EX-145H, which had been dried under reduced pressure at 105°C for 4 hours, was immediately added to the reaction vessel, heated, and reacted at 110°C for 2 hours.

After straining the resin from the reaction vessel, the reaction mixture was analyzed by gas chromatography and vacuum distillation.

The yield of monoalkylphenol based on olefin is 9
It was 7chi.

Instead of Diaion EX-145H, a typical commercially available strongly acidic polystyrene-based sulfonic acid type resin was treated in the same manner and added in portions. The results for each case are shown in Table 4.

Table 4 (Example 2) When the same method as in Example 1 was carried out using 105 parts of pentadecene (molecular weight 2) as the olefin, the yield of monoalkylphenol was 94%, and the yield of polyalkylphenol was 1.5%. It was a lot.

(Example 3) When the same method as in Example 1 was carried out using 84 parts of dodecene (molecular weight 168) as the olefin, the yield of monoalkylphenol was 91%, and the yield of polyalkylphenol was 3%.

(Example 4) The same method as in Example 1 was used to prepare an olefin with a carbon number of 20.
22.24.26 mixed olefins (molecular weight 336) 1
When carried out using 68 parts, the yield of monoalkylphenol was 89 parts, and the yield of polyalkylphenol was 4%.
Met.

(Example 5) Phenol 94 was added to the reaction vessel using the same apparatus as in Example 1.
．． 1 part, 115 parts of an olefin with a molecular weight of 231, and N
2 Heated to 60℃ in atmosphere, then heated to 105℃ under reduced pressure.
Immediately put 10 parts of Diaion EX-145H, which had been dried for 4 hours at
The reaction was carried out for 0 hours. The yield of monoalkylphenol based on olefin was 97%.

(Example 6) When the reaction was carried out for 1 hour at a reaction temperature of 145° C. in the same manner as in Example 5, the yield of monoalkylphenol based on the olefin was 97%.

(Example 7) A reaction was carried out in the same manner as in Example 2 using 40 parts of Diaion EX-145H, and the yield of monoalkylphenol was 99 parts.

(Example 8) The yield of nol was 90%.

Considering the above tests, it is clear from Examples I, 2.3 and 4 that the Diaion EX-145H according to the present invention
has 12.15 carbon atoms, ] 6 + 18.20 + 22 + 24
Monoalkylphenol can be produced from +26 olefin and phenol at high yields of 97%, 94%, 91%, and 89% based on the olefin, respectively.

Furthermore, as is clear from Examples 1.5 and 6, by adjusting the reaction time, 60°C, 110°C and 145°C
At a reaction temperature of , monoalkylphenol could be produced with a yield of 97%.

Regarding the amount of catalyst used, see Examples 1 and 8, and Example 2.
Comparing 7 with 94.1 parts of phenol and C16+
For 115.5 parts of cis mixed olefins, monoalkylphenol can be obtained with a high yield of 97% using 10 parts of catalyst (5 parts "C" is 90% yield), while phenol 94.1 parts and 015 olefins 1
If 10 parts of catalyst were used for 05 parts, monoalkylphenol could be obtained with a high yield of 94%. When used, monoalkylphenol can be obtained in high yield, the reaction temperature is flexible to some extent (preferably around 145°C), and the amount used does not need to be large, and of course it can be recycled. Therefore, it is highly economical.

Claims (1)

[Claims] When producing alkylphenol by reacting phenol with an olefin having 12 to 30 carbon atoms, a strongly acidic polystyrene-based sulfonic acid type cationic resin with excellent thermal stability and increased acidity is used as an alkylation catalyst. A method for producing monoalkylphenol, characterized by obtaining monoalkylphenol in high yield.