JPS5984830A - Preparation of diisobutylene - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as a raw material for preparing nonyl alcohol, etc. in high yield free from problems of corrosion of device, etc., by bringing ethylene glycol monotertiary butyl ether as a raw material into contact with a cation exchange resin of strong acid type as a catalyst under specific conditions. CONSTITUTION:Ethylene glycol monotertiary butyl ether is used as a raw material, and brought into contact with a cation exchanger catalyst of strong acid type at about 85-150 deg.C under pressure, more preferably conditions at about 3- 20kg/cm<2>.G, especially about 5-15kg/cm<2>.G, at about 100-130 deg.C at about 0.1- 5.0hr<-1> liquid space velocity, especially about 0.2-2.0hr<-1>, to give the desired compound. A cation exchange resin of styrenesulfonic acid type, etc. may be cited as the cation exchanger of strong acid type. Selectivity for the desired compound is more enhanced by using a mixture of the raw material with ethylene glycol than using it alone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diynebutylene from ethylene glycol monotadilyptyl ether.

In general, diimbutylene is a dimer of isoptylene, mainly 2,4.4-)limethylpentene-1
It is a mixture consisting of 2.4.4-)limethylpentene-2 and small amounts of other isomers. This diimbutylene is used as a raw material for producing octyl alcohol by hydration, nonyl alcohol by the Oquin method, octylphenol, etc., and it is easier to react with liquid diisobutylene than with gaseous imbutylene. Therefore, it is also used as a raw material for the production of butylphenol. In these cases, 2, 4.4. - Those with a high content of trimethylpentene-1 and 2,4.4-trimethylpentene-2 are preferred.

Conventionally, diimbutylene has been produced by bringing the C4 hydrocarbon fraction into contact with an aqueous sulfuric acid solution to polymerize the imbutylene in the C4 hydrocarbon fraction, and then separating and purifying the product. However, in this sulfuric acid method, in addition to the target diynbutylene, a large amount of oligomers such as triynebutylene and butrinebutylene are produced as by-products.
It reaches ~30%. Also, 2.
4,4-trimethylpentene-1 and 2,4.4-)
The content of remethylpentene-2 is as low as 92-96,
Another drawback is that it also contains dimethylhexene, which is a polymer of imbutene and normal butene, as impurities. Furthermore, since sulfuric acid is used, there is a problem of equipment corrosion, and the equipment must be constructed of expensive corrosion-resistant materials.

As a result of various studies, the present inventors discovered that the desired diynebutylene could be obtained with high selectivity by using ethylene glycol monotertiary butyl ether as a raw material and a strong acid type cation exchange resin as a catalyst. The invention has been completed.

That is, the gist of the present invention resides in a method for producing diimbutylene, which is characterized in that diisobutylene is obtained by contacting ethylene glycol monotertiary butyl ether with a strongly acidic cation exchanger catalyst at 85 to 150'C under pressure.

Ethylene glycol monoteralyptyl ether (hereinafter sometimes abbreviated as MBE) as a starting material may be used alone or in a mixture with other components such as a solvent or diluent. When MBE is used as a mixture with ethylene glycol, the selectivity for producing diynebutylene is higher than when used alone. M.B.E.
When used as a mixture with other components, if the MBE content in the raw material mixture is too low, the equipment capacity will increase;
Moreover, the amount of heat required will also be excessive. Therefore, the preferred content of MBE in the feedstock is about 5 parts by weight or more, especially about 5 parts by weight or more.
~80 weight section.

In addition, it is known that ethylene glycol monoturgyl ether can be produced by reacting ethylene glycol and an inbutylene-containing C4 hydrocarbon fraction in the presence of a strong acid type cation exchanger catalyst, for example, as disclosed in US Patent No. 24809.
No. 40, No. 3170000, No. 3288842, and Japanese Patent Publication No. 57-35687, etc., and the products are usually composed of the main product MBE and the by-product ethylene glycol dicoushaributyl ether (hereinafter abbreviated as DBE). ) and ethylene glycol. Therefore, this reaction product as it is, MBE separated from the product, or a mixture containing MBE can be used as the raw material of the present invention. In this case, even if DBE is contained in the feedstock, the content is small and the reaction temperature is high, particularly if it is above about ioor, both DBE and MBE are decomposed and diisobutylene can be obtained in high yield. Therefore, when DBE is included in the raw material mixture, the content should be about 0.40 parts by weight or less per 1 part by weight of MBE. If the DI3E content in the raw material mixture is too high or the reaction temperature is too low, the amount of MIlE in the system will not decrease, and the purpose of the present invention to obtain diisobutylene from MBE will not be achieved, and the yield of diisobutylene will also decrease. It becomes low.

Examples of strong acid type cation exchangers that can be used as catalysts include styrene sulfonic acid type cation exchange resins (sulfonated crosslinked copolymers of styrene and polyunsaturated 6-compounds such as divinylbenzene), and phenol sulfone. Acid-type cation exchange resins (phenol sulfonic acid condensed with formaldehyde), sulfonated coal, sulfonated asphalt, sulfonic acid-type cation exchange resins with sulfonic acid groups bonded to fluororesin (for example, DuPont Nafion, etc.) ) have a sulfonic acid group.

The reaction of contacting ethylene glycol monoturgyl ether with a strong acid type cation exchange catalyst to form diisobutylene is carried out at a temperature of about 85-150C and under pressure. Preferred reaction conditions are 2 to 2 at a pressure of about 3 to 20
・G especially about 5~1sKy/Kushi 2・G, temperature about 100~1
30 G, and the liquid hourly space velocity is about 0.1 to 5.0 hr-", especially about 0.2 to 2.0 hr-". If the pressure is too high or too low, the selectivity of diisobutylene will be low, and if the temperature is too low, the conversion rate of the raw material glycol ether will be low.
If the temperature is too high, the selectivity of diynbutylene will be low and the catalyst will be damaged.

If the liquid space velocity is too slow or too fast, the selectivity of diisobutylene will be low. Further, the raw material may be supplied to the catalyst bed in an upward flow or a downward flow, but it is preferable to supply the raw material in an upward flow because the produced diisobutylene has a small specific gravity and tends to collect upward. The reaction is usually carried out in a fixed bed system, but if necessary, it may be carried out in a moving bed system or a suspended bed system, and in addition to these continuous flow systems, it may also be carried out in a batch system. In the process of the invention, raw glycol ether is converted into diisobutylene and ethylene glycol.

Diisobutylene can be separated from the reaction product mixture by conventional methods. For example, if the resulting mixture is a homogeneous solution, it can be taken as it is, or if it has two layers, a diynbutylene-containing layer and an ethylene glycol-containing layer, the diynbutylene-containing layer can be separated, and this can be distilled, for example, or azeotropically distilled. Diynbutylene is separated and purified through operations such as , extractive distillation, and solvent extraction.

The effect of the method of the present invention is that the selectivity of the target diynebutylene is high and the production of triisobutylene and higher order oligomers is small. The selectivity of 2,4,4-1-dimethylpentene-1 and 2,4,4-)dimethylpentene-2 isomers, which are useful among diynebutylene, is particularly high. The selectivity of diisobutylene is still high, and the conversion rate of raw glycol ether is also relatively high. Furthermore, since the method of the present invention does not use sulfuric acid, there is almost no problem of equipment corrosion.The present invention will be explained below with reference to Examples.

Examples 1 to 6 In a reaction tube, 90CC of strong acid type cation exchange resin catalyst Amberlyst 15 (manufactured by Rohm and Haas) was used.

A sulfonated copolymer of styrene and divinylbenzene was packed with an exchange capacity of 4', 9 meq, /f + particle size of 0.3 to 1.0 mm), and this catalyst bed was charged with a catalyst having the composition shown in Table 1. The raw materials were passed in upward flow at the reaction conditions shown in Table 1.

These results are shown in Table 1. In addition, Examples 1 to 1 in Table 1
Example 5 shows the results 3 hours after the start of the reaction, and Example 6 shows the results 7 days after the start of the reaction. In addition, 2.4.4-trimethylpentene- in diynebutylene obtained in Example 1
The total content of 1 and 2.4.4-1-limethylpentene-2 was 99.6 wt%, and other isomers were mainly trimethylpentenes, and dimethylhexene was not observed. . The ratio of 2,4.4-trimethylpentene-1 and 2,4.4-trimethylpentene-2 was 77:23. The contents of 2,4,4-)limethylpentene-1 and 2,4,4-trimethylpentene-2 in the diisobutylene obtained in Examples 2 to 5 were also almost the same as in Example 1. Ta. 2.4.4-trimethylpentene=I and 21414-)+7methylpentene-2 in diisobutylene obtained in Example 6
The total content was 995% by weight, and the ratio of 2,4.4-trimethylpentene-1 to 2.4.4=trimethylpentene-2 was 76:24. Furthermore, in Examples 1 to 6, the products other than the inbutylene oligomer from MBE were mainly composed of inbutylene and ethylene glycol.

As shown in Table 1, in Examples 1 to 6, the selectivity for producing diisobutylene was high, the amount of by-products of higher oligomers of triynebutylene or higher was very small, and the conversion rate of MBE was also relatively high. . Still as mentioned above, the useful isomer 2,4°4-trimethylpentene in the diisobutylene produced
The content of 1 and 2,4.4-trimethylpentene-2 is very high. Furthermore, as can be seen from the results of Examples 5 and 6, the catalyst life is long.

Example 7 M B ID3 was added to the same reaction tube used in Examples 1 to 6.
3.4 wt% (22.7 mol%) + D B fL
A mixture consisting of 10.5 wt% (49 mol%) and 56.0 wt% (72.4 mol%) of ethylene glycol was heated to a temperature of 113C.

Pressure 5. □ K17cm2・G + liquid space velocity 0.4
The reaction was carried out for 4 hr'. The composition of the product is l'vI 13 E 20.9 wt%.

1] 3E3.9 wt%t ethylene glycol 65.0
w1%.

Inbutylene was 1.1 wt% and inbutylene oligomer g was 1 wt%. M in raw materials and products
Calculated from the molar ratio of BE, DBE and ethylene glycol, the conversion rate on a molar basis of the total amount of MBE and I)Bg was 42.0%. -! The selectivity of the isobutylene oligomer was 89%. The amount was almost the same as the result of Example 1.

Patent applicant: Maruzen Petrochemical Co., Ltd.

Claims (1)

[Claims] Ethylene glycol monotarsia Ij border/L/x
- A method for producing diisobutylene, which comprises contacting chill with a strong acid type cation exchanger catalyst under pressure at 85 to 150C to obtain diimbutylene.